JP2002179600A - Method for producing high-purity 3-chloro-1-propanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily, industrially and efficiently producing high-purity 3-chloro-1-propanol free from impurities including its ether modification by selectively chlorinating 1,3-propanediol with hydrochloric acid or a hydrogen chloride gas as the hydrogen chloride source. SOLUTION: This method for producing high-purity 3-chloro-1-propanol comprises the steps of reacting a hydrogen chloride source with 1,3-propanediol at 60-100 deg.C to obtain a reaction liquid containing 3-chloro-1-propanol and then extracting and removing impurities present in the reaction liquid with a hydrophobic organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing 3-chloro-1-propanol from 1,3-propanediol with high purity and high yield. High-purity 3-chloro-1-propanol is an industrially important compound as a useful raw material for medicines, agricultural chemicals, polymers and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for producing 3-chloro-1-propanol, a transesterification reaction of 1,3-chloropropyl acetate (Patent Document 24,366, West German Patent Application).
No. 02 specification) and a production method by addition of acrolein with hydrochloric acid followed by a reduction reaction (Japanese Patent Publication No. 52-42769). However, each of these methods is a two-step reaction, and the latter has a high production cost due to the use of expensive sodium borohydride as a reducing material, and is a constraint on industrial use.

On the other hand, as a simple method for producing 3-chloro-1-propanol, 3-chloro-1-propanol is reacted with 1,3-propanediol using hydrochloric acid or hydrogen chloride gas.
-Method for producing propanol (CS Marvel)
Et al., Organic Nick Shishishizu (Organic
Syntheses), Coll. Vol. I, 5
33-535 (1964)). However, this method is a reaction at a high temperature of 150 to 170 ° C., and the obtained chlorohydrin has a low selectivity in the production of a high conversion, and it is difficult to obtain 1,3-dichloropropane and bis (3-chloropropyl) ether. There is a problem that these compounds contain an ether compound and are difficult to remove by distillation. When 3-chloro-1-propanol containing a large amount of these ethers is purified by distillation, the yield of the target 3-chloro-1-propanol is extremely reduced, and a high-purity product cannot be obtained. In addition, when the conversion is low, the production amount of 1,3-dichloropropane and some impurity ethers can be reduced, but the yield is low and it is unsuitable as an industrial production method from the viewpoint of cost.

[0004] As described above, there has been a demand for a production method capable of easily and industrially obtaining high-purity 3-chloro-1-propanol in high yield.

[0005]

In view of the above problems, an object of the present invention is to provide a method for selectively chlorinating 1,3-propanediol using hydrochloric acid and hydrogen chloride gas as a hydrogen chloride source. An object of the present invention is to provide a method for easily and industrially efficiently producing high-purity 3-chloro-1-propanol containing no impurities such as ethers.

[0006]

Means for Solving the Problems The present inventors have developed a 1,3-
As a result of diligent studies on a method of selectively chlorinating propanediol to obtain high-purity 3-chloro-1-propanol, it was found that hydrochloric acid or hydrogen chloride gas as a hydrogen chloride source was used in the presence or absence of a specific catalyst. When chlorination is performed at a reaction temperature in the range of 60 to 100 ° C., 3-chloro-1-propanol can be obtained with good selectivity, and subsequently, the reaction solution is washed with a hydrophobic organic solvent such as toluene or pentane. Indeed, it is possible to easily remove impurities such as ethers, and as a result, it is possible to obtain the desired high-purity 3-chloro-1-propanol very efficiently by distillation. A method for producing 3-chloro-1-propanol was found, and the present invention was finally completed.

Hereinafter, the present invention will be described in detail.

The hydrogen chloride source used in the present invention includes:
Hydrochloric acid and hydrogen chloride gas can be used, and these can be used alone or in combination.

In this case, the amount of hydrogen chloride usually used is 1,3 which is the starting compound in order to increase the conversion.
-It is preferable to use 1-fold or more moles with respect to propanediol.
More preferably, 1.5 times the molar amount is used. On the other hand, the use of hydrogen chloride in an amount exceeding 1.5 times the molar amount may increase the amount of 1,3-dichloropropane produced as a by-product and the ether compound which is difficult to remove and which causes a problem.

When hydrogen chloride gas is used, the blowing speed is generally set on an industrial scale (for example, 5 to 20).
The blowing speed used in the range of 0 kg / m ³ · hr) does not affect the generation of impurities such as by-products.

The reaction temperature is preferably in the range of 60 to 100 ° C. in view of the reaction rate and the selectivity of 1,3-propanediol. At a low reaction temperature of less than 60 ° C., the reaction hardly proceeds, and under severe heating conditions exceeding 100 ° C., the amount of generated 1,3-dichloropropane and ether increases, and selection of 3-chloro-1-propanol is performed. This is not preferred because the properties are significantly reduced.

In the method of the present invention, the reaction can proceed sufficiently without using a catalyst. Furthermore, by performing the reaction in the presence of a catalyst during the reaction, the reaction can be allowed to proceed at a relatively low temperature, and an improvement in the reaction rate and selectivity is recognized.

When the reaction is carried out in the presence of a catalyst, the catalyst used may be, for example, β-type acidic zeolite, H-ZS
Examples thereof include Lewis acids such as zeolites such as M5 and halogen metal chlorides such as FeCl ₃ and ZnCl ₂ . In addition to these, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium fluoride, tetrabutylammonium fluoride hydrate, tetrabutylammonium sulfite, tetrabutyl Ammonium hydrogen sulfide, benzyltrimethylammonium chloride, benzyltrimethylammonium chloride monohydrate, benzyltrimethylammonium bromide, benzyltrimethylammonium fluoride hydrate, benzyltrimethylammonium hydroxide, benzyltrimethylammonium methoxide, tetraoctadecyl ammonium Bromide, tetra-octyl ammonium bromide, such as tetra-octyl ammonium fluoride 4
Grade ammonium salts and phosphonium salts such as tetraoctylphosphonium bromide can also be used as the catalyst. These catalysts can be used alone or in combination of two or more.

The amount of the catalyst used is preferably in the range of 0.1 to 10% by weight based on the weight of the starting compound 1,3-propanediol, more preferably 1 to 5%.
A range of weight% is preferred.

In the method of the present invention, after the chlorination reaction,
A hydrophobic organic solvent is added to the reaction solution, and impurities in the reaction solution are extracted and removed by the hydrophobic organic solvent. A known method and apparatus can be used for adding and extracting the hydrophobic organic solvent to the reaction solution.

As the hydrophobic organic solvent to be used, a solvent which is hydrophobic, does not substantially dissolve water-containing 3-chloro-1-propanol, and well dissolves the ether compound of impurities and 1,3-dichloropropane is selected. .

More specifically, such hydrophobic organic solvents include linear solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane and octadecane. And 2-methylbutane, 2-methylpentane, 3-methylpentane, 2-
Chain aliphatic hydrocarbons having side chains such as methylhexane, 3-methylhexane, 2-methylheptane, 2,2-dimethylhexane, and 2,3-dimethylheptane; cyclic hydrocarbons such as cyclohexane and methylcyclohexane Aromatic hydrocarbons such as benzene, toluene, o-, m-, p-xylene and ethylbenzene; dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chloropropane, 1,3-dichloropropane, 1,2-dichloropropane; n-butyl chloride, 1,4-dichlorobutane, 1,3-dichlorobutane, n-pentyl chloride, cyclopentyl chloride, n-hexyl chloride, cyclohexyl chloride, n-octyl chloride, n-lauryl chloride, dibromomethane, bromoform, Tetrabromo Tan, n-propyl bromide, i-propyl bromide, 1,3-dibromopropane, 1,2-dibromopropane, n-butyl bromide, 1,4-dibromobutane, 1,3-dibromobutane, n-pentyl bromide, Aliphatic halogen compounds such as cyclopentyl bromide, n-hexyl bromide, cyclohexyl bromide, n-octyl bromide, n-lauryl bromide; chlorobenzene, o-,
m-, p-dichlorobenzene, o-, m-, p-chlorotoluene, o-, m-, p-bromotoluene, α, α,
Aromatic halogen compounds such as benzotrifluoride; aliphatic esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate; aromatic esters such as methyl benzoate, ethyl benzoate and isobutyl benzoate Aliphatic ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, diisoaluminum ether, chloromethyl methyl ether, bromomethyl methyl ether; aromatic ethers such as anisole, phenetole, diphenyl ether, trifluoromethoxybenzene; Aromatic ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 3-methylpentenone; diethyl carbonate;
Carbonates such as di-t-butyl carbonate; olefins such as cyclohexene. Among these, chain aliphatic hydrocarbons, aromatic hydrocarbons, and aliphatic halogen compounds are particularly preferred. Each of these hydrophobic organic solvents can be used alone, but two or more of them can be used in combination.

It is sufficient that the amount of the hydrophobic organic solvent used in the extraction is 5% by weight or more based on the reaction solution. On the other hand, when the solvent is removed by washing using an amount of the solvent such that the amount exceeds 50% by weight, the desired 3-chloro-
1-Propanol may also be extracted and removed, reducing its yield. Therefore, the use of 5% to 50% by weight is more preferable. The number of extractions may be one,
It may be repeated with a small amount of solvent.

As described above, the hydrophobic organic solvent is added to the reaction solution, and impurities are extracted as an organic solvent phase. The organic solvent phase containing the impurities is removed by a separation means such as liquid separation. The removal method may be performed by a commonly used method and apparatus.

The phase containing 3-chloro-1-propanol from which impurities have been removed has a sufficiently high purity as it is, but in order to further improve the purity, this is distilled.
High purity 3-chloro-1-propanol can be taken up. Distillation conditions are not generally determined by commonly used methods and apparatuses, but are usually performed under reduced pressure conditions.
The distillation temperature may be any as long as the object of the present invention can be achieved.

[0021]

EXAMPLES The details of the reaction are described in the following examples, which do not limit the present invention. The product of this reaction was confirmed by GC-MS. In addition, all the yields were confirmed by analysis using gas chromatography.

Example 1 38.1 g (0.50 mol) of 1,3-propanediol
And 0.78 g (2.0% by weight) of H-ZSM5 were placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, placed in an oil bath, and stirred at an internal temperature of 80 ° C. with hydrogen chloride gas. 24 g (0.65 mol) were blown in for 17 hours to cause a reaction. As a result, 57.2 g of a water-containing reaction solution was obtained, the conversion of 1,3-propanediol was 92.6%, and the target 3-chloro-1-propanol was 34.2 g (0.36 mol). Rate was 72.4%. The contents of by-produced 1,3-dichloropropane and bis (3-chloropropyl) ether were 9.3% and 1.8%, respectively. Then, using 50.0 g of the aqueous reaction solution, 20.0 g (40% by weight) of toluene was added, and the mixture was stirred, allowed to stand still, separated, and then separated into 1,3-dichloropropane and bis (3-chloropropyl). The organic layer containing an ether body such as ether was removed. as a result,
The contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were 1.0% and 0.3%, respectively. Table 1 shows the yield, the conversion rate of the raw materials, the selectivity of the reaction, and the composition after treatment in each step (indicated by the area ratio by GC measurement) in each step.

[0023]

[Table 1]

Example 2 A three-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer was charged with 38.1 g (0.5 mol) of 1,3-propanediol and 0.78 g (2.0% by weight) of FeCl3. And put in an oil bath.
At 24 ° C., 24 g (0.65 mol) of hydrogen chloride gas was blown in for 11 hours to cause a reaction. As a result, the water-containing reaction liquid
8.7 g were obtained, the conversion of 1,3-propanediol was 96.0%, the target 3-chloro-1-propanol was 32.9 g (0.35 mol), and the yield was 69.5%. Was. The contents of by-produced 1,3-dichloropropane and bis (3-chloropropyl) ether were 1% each.
It was 6.1% and 3.2%. Then, using 50.0 g of the aqueous reaction solution, 20.0 g (40% by weight) of toluene was added, and the mixture was stirred, allowed to stand still, separated, and then separated into 1,3-dichloropropane and bis (3-chloropropyl). The organic layer containing an ether body such as ether was removed. as a result,
The contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were 3.1% and 0.7%, respectively. Detailed results are also shown in Table 1.

Example 3 152.3 g (2.0 mol) of 1,3-propanediol
Was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, placed in an oil bath, and stirred with an internal temperature of 93 to 96 ° C. at 88 g of hydrogen chloride gas (2.4 g).
Mol) for 11 hours. As a result, 239.5 g of a water-containing reaction solution was obtained, the conversion of 1,3-propanediol was 90.3%, and the desired 3-chloro-1-propanol was 117.8 g (1.25 mol).
The yield was 62.3%. The contents of 1,3-dichloropropane and bis (3-chloropropyl) ether produced as by-products were 17.6% and 1.6%, respectively. Then, toluene was added to 228.5 g of the obtained aqueous reaction solution.
1 g (20.2% by weight) was added, and the mixture was stirred, allowed to stand still, and subjected to liquid separation. The by-produced 1,3-dichloropropane and bis (3-
The organic layer containing an ether such as chloropropyl) ether was removed. As a result, the contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were 7.8% and 0.7%, respectively. When this water-containing reaction solution was distilled at a top temperature of 57 ° C./10 Torr, 92.3 g of the objective high-purity 3-chloro-1-propanol was obtained.
(0.98 mol), yield 51.0% (purity 99.0%,
1,3-dichloropropane 0%, bis (3-chloropropyl) ether 0.7%). Detailed results are shown in Table 1.

Example 4 266.4 g (3.5 mol) of 1,3-propanediol
Was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, placed in an oil bath, and stirred with an internal temperature of 93 ° C. to 98 ° C. and 153 g of hydrogen chloride gas (4.
2 mol) for 17 hours. As a result, 413.8 g of a water-containing reaction solution was obtained, the conversion of 1,3-propanediol was 93.9%, and the target 3-chloro-1-propanol was 200.5 g (2.13 mol).
The yield was 60.6%. The contents of 1,3-dichloropropane and bis (3-chloropropyl) ether by-produced were 22.2% and 2.4%, respectively. Then, using 2.5 g of the aqueous reaction solution, 1.0 g of toluene
(40% by weight), and the mixture was stirred, allowed to stand still, and separated to remove an organic layer containing by-products such as 1,3-dichloropropane and bis (3-chloropropyl) ether. As a result, the contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were each 4.2.
% And 0.5%. Detailed results are also shown in Table 1.

Example 5 Using 2.5 g of a water-containing reaction solution obtained in the same manner as in Example 2,
After adding 1.0 g (40% by weight) of heptane and stirring, the mixture was allowed to stand and separated, and then an organic layer containing by-products such as 1,3-dichloropropane and bis (3-chloropropyl) ether was removed. . As a result, the contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were 5.3% and 0.7%, respectively. Detailed results are also shown in Table 1.

Example 6 Using 2.5 g of the aqueous reaction solution obtained in the same manner as in Example 2,
After adding 1.0 g (40% by weight) of chlorobenzene and stirring,
After standing and liquid separation, an organic layer containing by-products such as 1,3-dichloropropane and bis (3-chloropropyl) ether was removed. As a result, the contents of 1,3-dichloropropane and bis (3-chloropropyl) ether were 5.5% and 0.7%, respectively. Detailed results are also shown in Table 1.

Comparative Example 1 266.4 g (3.5 mol) of 1,3-propanediol
Was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, and placed in an oil bath. The temperature of the oil bath was maintained at 165 ° C., and 134 g (3.7 mol) of hydrogen chloride gas was added while stirring. The reaction was carried out for 2.0 hours. Although water was generated as the reaction proceeded, the reaction was completed without removing water from the system during the reaction. As a result, the internal temperature gradually decreased from 160 ° C. with the generation of water, and finally decreased to 102 ° C. The composition of the obtained water-containing reaction solution was as follows. 1,3-
92.7% conversion of propanediol, 1,3 by-produced
The contents of dichloropropane and bis (3-chloropropyl) ether are 12.6% and 7.4% respectively;
The desired 3-chloro-1-propanol is 135.8.
g (0.95 mol), and the yield was 41.7%. Next, 380 g of the aqueous reaction solution was used, and toluene
g (40% by weight) was added, and the mixture was stirred, allowed to stand still, and subjected to liquid separation to remove an organic layer containing by-products such as 1,3-dichloropropane and bis (3-chloropropyl) ether. As a result, the content of each of 1,3-dichloropropane and bis (3-chloropropyl) ether was 1.8.
% And 1.6%. Table 2 shows the yield in each step,
The conversion rate of the raw material, the selectivity of the reaction, and the composition after treatment in each step (shown by the ratio of the area by GC measurement) are shown.

[0030]

[Table 2]

Comparative Example 2 152.3 g (2.0 mol) of 1,3-propanediol
Was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, placed in an oil bath, and stirred with 77 g (2.1 mol) of hydrogen chloride gas at an internal temperature of 55 ° C. for 13.4 hours. A blowing reaction was performed. As a result, 212.0 g of a water-containing reaction solution was obtained. In addition, the problematic impurities 1,3-dichloropropane and bis (3- (3-
The contents of chloropropyl) ether were 0.6% and 0%, respectively.
%, But the desired 3-chloro-1-propanol was 34.9 g (0.37 mol), the yield was 18.5%,
The conversion of 1,3-propanediol was 35.6%, and the starting compound 1,3-propanediol was 6%.
4.4% remained. Then, 200.0 g of the aqueous reaction solution
Then, 80.0 g (40% by weight) of toluene was added thereto, and the mixture was stirred, allowed to stand still, and separated to separate an organic layer containing an ether such as 1,3-dichloropropane and bis (3-chloropropyl) ether. Removed. As a result,
The contents of dichloropropane and bis (3-chloropropyl) ether were 0% and 0%, respectively. Table 2 shows the detailed results.

COMPARATIVE EXAMPLE 3 152.2 g (2.0 mol) of 1,3-propanediol
Was placed in a four-necked flask equipped with a reflux condenser, a thermometer and a magnetic stirrer, placed in an oil bath, and stirred with an internal temperature of 93 ° C to 95 ° C and 88 g of hydrogen chloride gas (2.4 g).
Mol) for 11 hours. As a result, 234.15 g of a water-containing reaction liquid was obtained, the conversion of 1,3-propanediol was 90.6%, and the desired 3-chloro-1-propanol was 115.1 g (1.22 mol), and the yield was 9 60.9%. Also, by-product 1,3
-The contents of dichloropropane and bis (3-chloropropyl) ether were 16.7% and 1.9%, respectively. Next, 223.4 g of the hydrated reaction solution was used without extracting and removing impurities in the hydrated reaction solution with a hydrophobic organic solvent.
Was distilled at a top temperature of 50 ° C./9 Torr. As a result, it was difficult to separate by distillation from bis (3-chloropropyl) ether, and 16.6 g (0.18 mol) of the objective high-purity 3-chloro-1-propanol was obtained. 99.1% purity, 1,3
-0% dichloropropane, bis (3-chloropropyl)
Obtained with 0.8% ether, the yield was 8.8%. Detailed results are also shown in Table 2.

When Examples 1 to 6 and Comparative Examples 1 to 3 are compared, impurities can be removed by extracting the reaction solution with a hydrophobic organic solvent after the chlorination reaction, as in the Examples, and high yields can be obtained. It was found that a highly pure 3-chloro-1-propanol was obtained at a high rate, and the purity could be improved by further distilling the 3-chloro-1-propanol. On the other hand, as can be seen in the comparative examples, unless the reaction solution is extracted with a hydrophobic organic solvent, not only high-purity 3-chloro-1-propanol is obtained, but also the distillation cannot be performed well. It can be seen that the yield is poor.

Example 7 Using 2.5 g of a water-containing reaction solution obtained in the same manner as in Example 4, the amount of toluene used for extraction was reduced to 0 g and 0.25 g (1
0% by weight), 0.5 g (20% by weight), 1.0 g (40% by weight).
% By weight), stirred, and allowed to stand still for liquid separation.
3-dichloropropane and bis (3-chloropropyl)
The organic layer containing an ether body such as ether was removed.
As a result, the contents of bis (3-chloropropyl) ether were 2.00%, 1.57%, 0.90%, respectively.
%, 0.51%.

From this, it can be seen that the extraction effect of toluene increases the extraction rate, ie, the removal rate of ethers such as 1,3-dichloropropane and bis (3-chloropropyl) ether, depending on the amount added. .

Example 8 Using 2.5 g of a water-containing reaction solution obtained in the same manner as in Example 5, the amount of heptane used for extraction was reduced to 0 g and 0.125 g.
(5% by weight), 0.25g (10% by weight), 0.5g
(20% by weight), and 1.0 g (40% by weight) were added, stirred, left to stand, and separated to contain by-produced ethers such as 1,3-dichloropropane and bis (3-chloropropyl) ether. The organic layer was removed. As a result, the screw (3
-Chloropropyl) ether,
2.00%, 1.44%, 1.22%, 0.98%,
It became 0.72%.

From this, it can be seen that the extraction effect of heptane increases the extraction rate, ie, the removal rate of ethers such as 1,3-dichloropropane and bis (3-chloropropyl) ether, depending on the amount added. .

Example 9 Using 2.5 g of a water-containing reaction solution obtained in the same manner as in Example 6, the amount of chlorobenzene used for extraction was reduced to 0 g and 0.5 g.
(20% by weight), and 1.0 g (40% by weight) were added, stirred, left to stand, and separated to contain by-produced ethers such as 1,3-dichloropropane and bis (3-chloropropyl) ether. The organic layer was removed. As a result, the screw (3
-Chloropropyl) ether,
2.00%, 1.21% and 0.66%.

From the above, it can be seen that the extraction effect of chlorobenzene increases with the extraction rate, ie, the removal rate of ethers such as 1,3-dichloropropane and bis (3-chloropropyl) ether, depending on the amount added. .

[0040]

According to the method of the present invention, high-purity 3-chloro-1-propanol, which is an industrially important compound, is an inexpensive starting compound as a useful raw material for medicines, agricultural chemicals and polymers. This production method is useful as an industrial production method of high-purity 3-chloro-1-propanol because it can be easily and efficiently obtained from 1,3-propanediol.

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Claims (5)

[Claims] 1. A reaction solution containing 3-chloro-1-propanol by reacting 1,3-propanediol with a hydrogen chloride source at 60 to 100 ° C. Then, impurities present in the reaction solution are subjected to hydrophobic treatment. A method for producing high-purity 3-chloro-1-propanol, which comprises extracting and removing the compound with an organic solvent. 2. The method for producing high-purity 3-chloro-1-propanol according to claim 1, wherein distillation is performed after extraction and removal. 3. The hydrophobic organic solvent is one or more selected from the group consisting of hydrocarbons, halogenated hydrocarbons, esters, ethers, ketones, carbonates and olefins. The method for producing high-purity 3-chloro-1-propanol according to claim 1 or 2, characterized in that: 4. The method according to claim 1, wherein a hydrogen chloride source is reacted with 1,3-propanediol in the presence of a catalyst.
3. The method for producing high-purity 3-chloro-1-propanol according to any one of 3. 5. The method according to claim 4, wherein the catalyst is one or more selected from the group consisting of zeolites, halogen metal salts, quaternary ammonium salts and phosphonium salts.