JPS6041631A - Cyclization of ortho-benzoylbenzoic acid - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to olumbenozoylbenzoic acid (osom). Activated bleaching soil (5upcractive hlcarhin)
g earN+;ferry decolorantc
5super-active) For example, it relates to a method for producing anthraquino-7 by cyclization in the presence of activated clay.

01313 acid? r aillI: e i or fuming sulfur U
It is known to produce anthraquinone r by heating in the presence of (olcum). Such methods include, for example, Ar+hur 1. Vogel VC: J
: 9 - +1rarLical OrsanicO
hcmi s try'', 3rd edition, 6z 7 ii O
Reported to LE. Sulfur lj deficiency plays a role as a catalyst and a reactive medium.

17 (Dfj acid is pure g′1 acid or phosphorus pentoxide with Eri1
I can do t1 chivalry.

In each of the methods, large amounts of reactants are used, which reduces the efficiency of the corresponding reactions and causes the problem of waste acidic materials and severe IJJ environmental pollution.

In Japanese Patent Application No. 7.260/1984, a method using a smaller amount of sulfuric acid is proposed by FH, but this method requires too much effort! It is safe to carry out the two-boosting at a temperature above about 300° C. - this poses operational hazards and the consequences of such a reaction! The corrosion inherent in one condition increases the cost of equipment i'i:819. Furthermore, the recovery of the produced Anotra.None by sublimation can only be carried out after neutralization of the sulfuric acid with carbonic acid.

U.S. Patent No. 21g, J 4.2 Smaller amount of sulfuric acid for the lightest females? The method to use is listed on h1.

In this way, IrJ, OB D I”72(f) closed fM
(+Ia conversion) ir, 2boC, like trichlorbenhine, ? The water produced during the reaction is distilled in the presence of a bath agent and the water produced during the reaction is co-distilled with a third spreader (in the form of a filtrate mixture). The equipment is complicated and the use of this bath agent +
d. Anotraquinone r Steam distillation VCL separation is uneconomical because it must be recovered.

US 1st license 2nd. / 79. ／／The most detailed statement (,
, ) B BI:' It has been proposed to use hydrogen fluoride as a cyclization catalyst for PI VC. However, the use of such a reactant has major drawbacks due to its V-quality; namely, corrosion by the water/hydrogen fluoride mixture formed during operation, dehydration of this mixture, etc. The drawback of Pf is that it is safe to perform the recovery under OBI'3 [shun's closed t1.'l f ratio].

US IJIiH'F ti, y o q, 7.27 most light A
:llI '+, '-J' U is an inert Ii (1°1 Thiζb in the U agent, ξ-Fluorinated I fat? The method of manipulation and use as a catalyst is described. With this method, lv! medium can be easily recovered, but Of+
The conversion to 13 and the yield of anthraquinone are low;
For example, C, 60% and 7g%, respectively,
The reaction is divided into anthraquino 7 from if (M agent) i'ii
i:'It's safe to do it while being L.

'f&1ffl昭'l 9-6.2 <t t) ゛For details-4 bow, it is recommended to heat at 360℃ in the presence of active 1'E clayVCj: f)0[3BIVke ring closure I'm at Sashi 1, but this method requires operation K.
It is essential to do this with A-button.

Slow ring closure rate; use of an intimate mixture of OBB acid and active 1-1 clay? Requires: 9 [and almost all of the anthraquinone produced by I to be absorbed by the active cell L1 Hikrei VC.The actual yield is low compared to vCL: 9
Has some drawbacks. In order to recover the anthraquinone 7 that has been cured by scent absorption, it is necessary to perform an expensive extraction operation consisting of (1) extracting the anthraquinone from the clay using a shell f + ': agent, and (2) evaporating the anthraquinone using a bath salt. There is.

French utility model 5 flood 7 Otsu, / g 9 J 6 11.1 〒) (Publication number → ;, 2...? / tt, 9
T,? OB 13 f'
i:? By heating l−+(1 with 2 aluminum, 0131.1 i'+n i
l cane - 1' is 1, self 11ζ1 is being used. If this reaction is carried out in a liquid state, the reaction may be carried out in a fixed bed or in a stream (11J).
Regardless of whether the process is carried out in bed,
The subsequent removal of the acclimating medium is difficult and expensive. In the first method! (There is a risk of rapid clogging of J, l, and it is difficult to separate the catalyst from the fine particles of a/traquinone in the second method.) The ratio is given when the latter method is carried out under vacuum.

The present invention eliminates the drawbacks of known methods.

9 If the present invention is oBsew cyclized, will it be possible to obtain anthraquinone? In generating it, the above OBB Rokuke is about JOO~
Activated bleaching soil (5u
pera1. tive bleaching l:,]
rtb:terre b4colorante 5LI
heating in the presence of per-active )?
The present invention provides a method for cyclizing OBB acid characterized by its characteristics.

Furthermore, the present invention [according to the above-mentioned *Os B mt
v cyclization? A method for removing phthalate moieties from 4fl VC013B 6% is also provided.

The term ``activated bleaching soil'' refers to clays of the bentonite type and which have been reacted with mineral acids according to known methods, washed with water such that the acid content of the salt, coated as hydrochloric acid, does not exceed 0,/ππ. Final VC/) 0°C This is a term recently used for drying at a non-toxic temperature. .

According to the method of the present invention, the conversion of OBB acid can be carried out without using an intimate mixture of this compound and active clay, and cyclization yields of 90π or more can be obtained. In general, an operating time of 8 to 7.20 minutes, often 5 to 60 minutes, is sufficient.

As for temperature, OB at temperatures above 1 Ioo℃
However, at temperatures below 100° C., where multi-digit benozophenones are produced, a long reaction time is required, making it economically advantageous.

The discharge of bleaching soil is ORB acid / 71 (per f7f part, usually 0.,!;-,31 parts, suitable for trenching 7-3
Parts by weight.

Preferred live bleaching soils suitable for use in the process of the invention have the following composition (%): 5i0270 Zhao-7j %, A I2O3/ (:l
%~-2(1)%, F" e2033%~j%,
Mg('J/%~3%, Oao 0.!t, 2
Substances that can be removed by the kidneys, labor, time, and time J crab ~ 70 crab.

An aqueous suspension containing 0% p of this type of active product white soil care
ll is fishing. Often 150 microns (μm)
) The specific surface area of such compounds present in the form of particles of smaller size is approximately /30-20 On? /V.

For example, with the product name "T ON 8I L"
- The method of the present invention can be used by simply adding a layer of 014 B acid to the active product commercially available from OtlEMIE.
: VC activation method: Setting up a layer of whitening soil can be done using VC. The thickness ζ of the layer of activated bleaching soil must be such that it fully allows for rapid diffusion of the anothrachinoforms formed during heating. Anothraquinone can be condensed according to known methods to sublimate 1 cL from the reaction medium for minutes W; fR.
v can be collected. To prevent condensation of water and volatile organic impurities, they can be collected, for example, on an anthraquinone ligature at a temperature of /θ0 to /30°C.

The anthraquinone collected by oxidation has high purity.

The method of the invention can be carried out continuously with discontinuous VC. A continuous method is carried out, for example, by the following method; ie, a constant, 1! Move horizontally at 6 degrees! Sipping stainless steel conveyor belt -☆: j3, bath melt Q 1
A layer of (,) B B rr support formed from 113 acid is provided, and on this layer I'l of Katsuchuhin White Clay:? k
Mj2ke, then the above-mentioned Conobear belt [that;fA l
il &I'': move along the continuous Fje target V and in the meantime, raise the temperature of the /! / ! This is carried out by compressing on a second conveyor belt held at a temperature of -0°C and moving parallel to the main conveyor belt. The end of the main conveyor belt where the OB rl acid was loaded was regenerated by creating a vacuum with one part of the fan 91 (j), and the reaction step "I"
T q'(1jfF,'j fi seti;).

OB B acid (ha, carriage-like/Ii is also done frequently)], Rugotogu, this? IO: For example, by condensation of fucuric anhydride and benozeno according to the method described in f-VcMI2 in No. 77 f)
When 31 ml is prepared, it usually contains 7-talic acid and 7-talic anhydride as impurities.

The concentration of phthalic acid or phthalic anhydride can reach 10 kg.

Accordingly, a second object of the present invention is to provide a method for separating phthalic anhydride from 0B13 acid using VC before agglomeration, or separately from VC.

This method is based on the phthalic acid contained in 08B9. Cyclization to form phthalic anhydride, and then this? Phthalic anhydride originally present in the 08B acid (if present)
and in the presence of a 37% active soil as mentioned in the explanation for the chlorination of 0BI3 acids, at a temperature, preferably at the following temperature, i.e. LII of 0 13 r3 acid carried out! Transformation? Occurs during temperature rise taking into account. It consists of separation from the reaction medium by heating VC during the heating step at a temperature of 200-23-0°C.

The cyclization time of phthalic acid is usually 1 to 30 minutes.

Other terms of operation, such as the proverb ``Katsuhite Tsuhakuyo Yoni'':
is the reliability stated for the method VC used in the cyclization of 0BBtj2.

7 in the form of phthalic anhydride during the cyclization of the OBB acid
The finding that 0[3L (the molecules of phthalic anhydride originally present in the acid, l'ft) for thalic acid and the extent to which it is present is of magical and industrial interest.

Pre-existing phthalic anhydride is added to the phthalic anhydride produced from phthalic acid, for example, from 0 to 100.
01313 t', which was recovered by condensation according to the method of 1,
It can be advantageously recycled for the production of f.

The above method of the invention can be carried out batchwise or continuously.

In a continuous process, the OBB acid is continuously cyclized on a conveyor belt, containing phthalic acid and, if present, phthalic anhydride.
+8! And a layer of active party white soil? The superimposed layers of 2p:j are heated to 200-2.50° C. during the movement of the belt to cyclize the phthalic acid to phthalic anhydride, and the formed phthalic anhydride If present, it is sublimed together with the phthalic anhydride already present in the OBB acid and collected on a conveyor belt located above the main belt 11 (fc).

Examples of the present invention are shown below.

Examples / OBB acid in powder form 2.701 Reference number BW, ? of[
TONSILJ 6. ,? 0? and mix roughly at low temperature. This mixture was placed at the horizontal bottom of a cylindrical futsutsukuda container with a diameter of go and a height of isrrrm. Stm is deposited in the form of 7 layers of practically uniform JF,I thickness. This layer? Cover with one piece of stainless steel wire mesh. Rustless steel lid? The container is then immersed in a molten metal bath, heated to a temperature of 100°C and maintained at this temperature for 6 minutes.During this operation, the temperature of the lid is approximately 100°C. It is. After removing the container from the heating bath and cooling, anotraquinone 2.3/? "z can be collected on the lid and the wire mesh, thus collecting crystals of anthraquinone that can be exfoliated from the lid. These anothraquinone 2.31? are the ?
The cyclization yield was 3.0%.

Example) ,? At a temperature of 00°C/I1. 〒j1 (Other than 1 operation, the actual operation is 9 as in Example 1.
．． I collected 26V, which is 90. g Represents the agglomerated yield of crab's OBB acid r.

Example 3 o1313 ("Rq, j'
/and? By operating as in Example 1, anotraquinone, ? , 77 r i got, this is 9/,
0% OBs acid cyclization yield.

Example: Melted OBB acid in a container of 2.70 ? /layer'f
r: deposited, allowed to cool and solidify at room temperature, and then the same bleaching soil as in Example 1 6.37
is deposited in a single layer of virtually uniform thickness.

Then implementation f! /lJl, anthraquinone 2. ．． 3 j SF i collected and this is OB
EXAMPLE J Compound containing 90% OBB acid and IO% 7-talic acid 2.7 ? In the molten state, the diameter gOrtan
, height/, 5ran, at the bottom of a cylindrical stainless steel container. After cooling and assimilation of the scented layer,
On this layer vc, one layer of practically uniform thickness of commercially available activated M white soil 6.31 manufactured by S [JDO) IEMIFi A, G, Inc. vc under the commercial name of oNsILJ reference number BW3 is provided. .

The container was covered with a lid made of stainless steel, immersed in a molten metal bath, heated to 9.2 JO°C, and held at this temperature for 6 minutes. During this period the temperature of the lid is approximately 70°C; at the end of this period the lid is removed and another lid is used in its place, this new lid is then subjected to the chemistry of 088 acid under the conditions described above. It is useful for collecting anthraquinones.

, ZAiO When the lid r is removed following the heating step at 0,
/, r When the sublimate of r is collected and analyzed by thin layer chromatography, is it actually only phthalic anhydride? Indicates that it contains only a name.

Comparative Example 1 By treating as in Example J except that no active bleaching soil was used, only 7 phthalic anhydride crabs, which were previously recovered in Example J, were collected.

Fruit 4 Example 6 A compound containing go@flying crab's Or313 acid, io heavy fti crab's phthalic acid, and / 0@combing crab's 7-talic anhydride? By processing as in Example S except for use, 0
．． 1AI1. ? 4), which contains virtually no VC containing only phthalic anhydride.

Ratio example: 67% of the phthalic anhydride recovered in Example 6 was treated as in Example 2 except that no bleaching soil was used.
Only π can be obtained.

Example 7 ``OBB acid of yo heavy bone π, phthalic acid of S weight crab and quintuple,
Ye Zhao's phthalic anhydride? Using the compound containing A and 12
The process was carried out as in Example J, except that the heat treatment was carried out at 30° C. for 1 min. r
(i-Recover.

Although the invention has been described in terms of preferred embodiments, this is not intended to limit the scope of the invention to the specific forms described, but to the contrary, it is intended that It is intended to include alternatives, modifications, and equivalents.

Claims (1)

Claims: 4. In a solid phase at atmospheric pressure at a temperature of about 300°C to 900°C in the presence of a solid activated bleaching soil for a period sufficient to cyclize substantially all of the orthobenzoylbenzoic acid to anthraquinone. Orthobenzoylbenzoic acid 112 A process for the cyclization of orthobenzoylbenzoic acid to anotraquino/, which comprises total heating. 2 The above activated bleaching soil is 70-7J direct 8'A'% 5
i02 and lo-20 weight crab A7203? -J fish phrase% l? e203 and' ~3 weight jK % MgO and 0
-j -2jlj j%i: %(1a (J and 3-
Contains ~1orKf&% of substances removed by calcination, about /! Ran? /? ~, 20On? /? A method according to claim 1, wherein the method is formed from fine particles having a specific surface area of , and dimensions of less than or equal to ISOμ. 3 Orthobenzoylbenzoic acid and activated bleaching soil? 3. A method as claimed in claim 1 or claim 2, in which the anotraquinones formed and sublimed are mixed or layered together to such a thickness that all the anothraquinones formed and sublimed are completely diffused over said acid and active. Hiroshi: The active bleaching soil used had a pH of about 11 for each of the above acids [approximately 0 per foot, s - y position, and the reaction time was approximately 5
3. The method of claim 7 or 2, wherein the duration is 720 minutes. Before the cyclization of orthobenzoylbenzoic acid, the acid is completely treated to remove any 7-tal C function contained therein, and the above treatment is performed by deactivating the phthalic acid ring to form phthalic anhydride. orthobenzoyl benzoic acid in the solid phase at atmospheric pressure to a temperature of about 200 to 50° C. 6. The method according to claim 1, which comprises heating the benzoyl benzoic acid and removing phthalic anhydride, 6. The reaction time for cyclizing the 7-thalic acid is 200-2
The reaction time is about /-, 30 minutes at j0°C, and the above reaction is orthobenzoylbenzoic acid? The IC degree is about 300 to cyclize.
The method according to claim 3, which is carried out during a certain period of time while the temperature is being raised to QOO°C.