CN105777705B - A kind of heliotropin intermediate synthetic reaction post-processing method - Google Patents
A kind of heliotropin intermediate synthetic reaction post-processing method Download PDFInfo
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- CN105777705B CN105777705B CN201610205663.6A CN201610205663A CN105777705B CN 105777705 B CN105777705 B CN 105777705B CN 201610205663 A CN201610205663 A CN 201610205663A CN 105777705 B CN105777705 B CN 105777705B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
- C07D317/60—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
The invention discloses a kind of heliotropin intermediate synthetic reaction post-processing methods, solid product is gradually produced in reaction mixture and gradually become viscous after dropwise addition piperonyl cyclonene, open the bottom valve of reaction kettle, blowing starts motor, opens the hot water entrance of chuck into auger, material is by the stirring of auger and heating for chuck hot water, accelerate reaction while moving ahead, when material arrives at auger outlet, reaction terminating.The material for leaving auger enters elutriation kettle, continues stirring 15 minutes, blowing centrifugation, mother liquor neutralisation treatment, filter residue is 3,4 methylene-dioxy mandelic acid of reaction product.The configuration of the present invention is simple, by increasing auger, form it into the pipeline reactor of a serialization, by the temperature for adjusting rotating speed and hot water, the reaction mixture material in arrival auger exit is set just to be close to or up to reaction end, it solves the problems, such as that the stirring of reaction later stage is difficult, piperonyl cyclonene and glyoxalic acid is enable smoothly to realize large-scale industrial production for the technique of main material.
Description
Technical field
The present invention relates to a kind of heliotropin intermediate synthetic reaction post-processing methods.
Background technology
Heliotropin also known as piperonal, heliotropine, heliotropin, piperonal, 3,4-methylenedioxybenzaldehyde etc., chemical name are
3,4-methylenedioxybenzaldehyde, English name are：piperonal、helitropine、3,4-
Methylenedioxybenzaldehyde, structure are as follows：
Molecular formula is：C8H6O3
Molecular weight is：150.13
C：64.00%, H：4.03%, O：31.97%
Heliotropin appearance is the glittering crystallization of white, 37 DEG C of fusing point, 263 DEG C of boiling point；It is insoluble in water and glycerine, is soluble in second
Alcohol, ether, Ergol, diethyl phthalate, dissolve in propylene glycol, in olive oil.Heliotropin is by light and heat
According to lower easy discoloration, stablize in diluted acid, diluted alkaline.
Heliotropin is a kind of intermediate of highly important fine chemicals and perfume synthesis, in food, daily chemical industry
With very wide application, most important purposes is used as the deodorant tune of various essence and flavoring agents.
Heliotropin finds during studying alkaloid-pipering (piperin) earliest, heliotrope,
There is a small amount of presence in the plants essential oils such as locust tree, fragrant folder beans, pepper, but very uneconomical from extraction is wherein directly separated.Therefore ocean
Jasminal is entirely produced by from the semi-synthetic technology of plants essential oil almost without all-natural product.It is almost all of at present
Heliotropin product is all from the semi-synthesizing technology using safrole as raw material.Semi-synthetic technology is mainly by safrole through isomery
Change, two step chemical reaction processes of oxidation are processed into heliotropin, are the industrialized productions of current natural material synthesizing piperonal
Process route.
Fully synthetic there are many ways to prepare heliotropin (piperonal), most of synthetic method raw material is easy to get, technique
Simply, it may be implemented industrialized production, almost all of method will be via 3,4- methylene-dioxies mandelic acid among this
Body.Wherein, most important method is to use piperonyl cyclonene and glyoxalic acid for main material, and under concentrated sulfuric acid catalyst, reaction generates intermediate
Body 3,4- methylene-dioxy mandelic acids, then 3,4- methylene-dioxy mandelic acids use is suitable oxidizing at heliotrope
Aldehyde.When synthesizing 3,4- methylene-dioxy mandelic acids, it is common practice to：A certain amount of acetaldehyde is first added into reaction kettle
Acid is slowly added dropwise to the concentrated sulfuric acid for preparing required concentration in advance according to the ratio again under stirring, with cryosel water cooling, control in kettle and mix
2~5 DEG C of sour temperature, drips required piperonyl cyclonene according to the ratio in 2~4 hours.After piperonyl cyclonene drips, reaction mixture continues
It is stirred to react about 24 hours, until the content of piperonyl cyclonene in mixed liquor no longer declines, termination is reacted.It is added into reaction kettle suitable
The water of amount, stirring, blowing filtering, solid is exactly 3,4- methylene-dioxy mandelic acids, and filtrate is dilute sulfuric acid, goes neutralisation treatment.
This process seems easy, but implements and remarkable, is gradually generated in reaction mixture after piperonyl cyclonene because starting to be added dropwise
Solid product simultaneously gradually becomes viscous, and the early period of reaction still can well stir；In the later stage of reaction, material is more and more sticky in kettle,
Stirring becomes more and more difficult, and until being fixed up, entire reactant is at a briquetting body.But at this point, internal reaction is simultaneously
Do not stop, and external cooling has been failed substantially, temperature of charge increases rapidly.With the raising of temperature of charge, it is adjoint and
The impurity in products of the side reaction and side reaction that come is more and more, had not only consumed raw material but also had increased the difficulty of post-processing.Therefore, when
Stirring can only be as early as possible toward ice water, force termination reaction be added in kettle after stagnating.
Invention content
Present invention aims at being provided for deficiency of the prior art, a kind of heliotropin intermediate synthesis is anti-
The technical solution for answering post-processing method stirs increasingly to solve 3, the 4- methylene-dioxy mandelic acid synthetic reaction later stages
Difficult problem.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of heliotropin intermediate synthetic reaction post-processing method, it is characterised in that include the following steps：
1) discharge outlet first below reaction kettle bottom valve increases an auger, and the feed inlet of auger is made to be directed at reaction kettle
Discharge port, and be smaller than 5cm between feed inlet and discharge port, elutriation kettle, elutriation then be set in the outlet end of auger
Kettle is located at 10~20cm of lower section of the outlet end of auger；
2) glyoxalic acid is then added dropwise into reaction kettle, and is at the uniform velocity stirred with the speed of 40r/min, then according to the ratio 3:1
The pre-configured concentrated sulfuric acid is added dropwise, is cooled down with brine ice, and controls the nitration mixture temperature in reaction kettle at 2~5 DEG C, 2
According to the ratio 2 in~4 hours:(1.5) required piperonyl cyclonene is added dropwise；
3) start to be added dropwise and gradually generate solid product in reaction mixture after piperonyl cyclonene and gradually become viscous, when mixed liquor
Viscosity reaches 50~80mm2When/s, the bottom valve of reaction kettle is opened, so that mixed liquor is passed through discharge port and is discharged in auger, is started
Driving motor on auger, and the rotating speed of driving motor is adjusted by frequency converter, while by the chuck hot water inlet on the outside of auger
External water tank is connected with chuck hot water outlet, hot water is made to enter in chuck, and hot water heating is the reaction in order to accelerate reaction rate
Early period, reaction all carried out at low temperature in kettle, and reaction speed is partially slow, if into continuing after auger to use low-temp reaction, auger
Length can be very long, it is improper, after material flows into auger, by hot water in the stirring of auger inside spin conveying lever and chuck
Heating accelerates reaction while moving ahead, passes through the first temperature inductor, second temperature inductor and the third temperature inside auger
The temperature difference for spending sensor measurement, is in real time adjusted the temperature of the rotating speed of spiral conveyor rod and hot water, so that material is arrived at and twists
Reaction terminating when imperial outlet end；
4) leave the material after auger and be directly entered elutriation kettle, the water of 1000ml is previously added in elutriation kettle, when material into
It is diluted after entering, while terminating reaction, after all reaction masses enter elutriation kettle, continue to stir 15min, you can will mix
It closes solution by vomit pipe to enter in centrifuge, the rotating speed for controlling centrifuge is 300~500r/min, centrifugation time 15min；
5) mother liquor after centrifugation is neutralized, and processing is dried in filter residue, obtains required reaction product 3,4-
Methylene-dioxy mandelic acid.
Further, the auger in step 1) is made of acidproof material, can effectively prevent inner wall of the concentrated sulfuric acid to auger
It causes to corrode with spiral conveyor rod, and then influences the normal work of auger, auger is equivalent to the duct type reaction of a serialization
Device carries agitating function and heating function, by adjusting the temperature of rotating speed and hot water, up regulation can react speed to a certain degree
Degree, makes the reaction mixture material in arrival auger exit just be close to or up to reaction end, and it is difficult to solve the stirring of reaction later stage
The problem of, so that piperonyl cyclonene and glyoxalic acid is smoothly realized large-scale industrial production for the technique of main material.
Further, the auger in step 1) is obliquely installed in the ゜ of 15 ゜~30, and material can not only be reduced by, which being obliquely installed, is passing
Resistance when sending, and liquid can be effectively prevent to be flowed out from feed inlet, safety is improved, driving motor energy is reduced
Loss.
Further, the centrifuge in step 4) is internally provided with centrifugal barrel, and centrifuge is divided into solid-liquid and mixed by centrifugal barrel
Chamber and liquid storage chamber, centrifugal barrel include filtering screen and chassis, and filtering screen is fixedly connected on the top surface on chassis, centrifugal barrel
Lower section be provided with pedestal, be provided with centrifugation motor in pedestal, centrifugation motor is by shaft connecting base plate, on the inner wall of centrifuge
At least two balance rings are provided with, centrifugal barrel rotation is driven by centrifuging motor, so that mother liquor is detached with filter residue, improve 3,
4- methylene-dioxy mandelic acid organic efficiencies, balance ring can make centrifugal barrel keep balancing when rotated, prevent due to shake
And influence the service life of centrifuge.
Further, the spacing between balance ring and filtering screen is 2~5mm, and the gap of 2~5mm can reduce balance ring
Frictional force between filtering screen improves the rotary speed of centrifugal barrel.
Further, it is provided with feed hopper and escape pipe on the top surface of centrifuge, the material after auger conveys passes through charging
Bucket enters in centrifuge, and the gas that escape pipe generates when can be by centrifugation discharges, and improves safety when centrifugation.
The present invention is by adopting the above-described technical solution, have the advantages that：
1, by increasing auger, the pipeline reactor of a serialization is formed it into, with agitating function and heating work(
Can, by adjusting the temperature of rotating speed and hot water, can up regulation reaction speed to a certain degree, make the reaction in arrival auger exit
Mixed material is just close to or up to reaction end, solves the problems, such as that the stirring of reaction later stage is difficult, makes the piperonyl cyclonene and glyoxalic acid be
The technique of main material can smoothly realize large-scale industrial production；
2, the setting of hot water jacket can accelerate the speed of reaction, while shorten the length of auger, be easily installed, and improve
Practicability, while reducing the generation of side reaction, the impurity of side reaction generation is reduced, reduces the loss of raw material, is simplified
The difficulty of post-processing；
The configuration of the present invention is simple increases an auger by the exit below reaction kettle bottom valve, while outside auger
Increase chuck, and be passed through hot water in chuck, effectively prevent after piperonyl cyclonene in reaction mixture gradually it is chromogenic be sorry consolidate
Body product becomes viscous, and keeps reaction more abundant, improves the separative efficiency of mother liquor and filter residue, so as to get product purity higher.
Description of the drawings
The invention will be further described below in conjunction with the accompanying drawings：
Fig. 1 is a kind of process flow chart of heliotropin intermediate synthetic reaction post-processing method of the present invention；
Fig. 2 is the structural schematic diagram of centrifuge in the present invention.
In figure：1- reaction kettles；2- elutriation kettles；3- augers；4- chucks；5- chuck hot water outlets；6- chuck hot water inlets；7-
Discharge port；8- feed inlets；9- spiral conveyor rods；The first temperature inductors of 10-；11- second temperature inductors；12- third temperature
Inductor；13- driving motors；14- vomit pipes；15- centrifuges；16- feed hoppers；17- escape pipes；18- pedestals；19- centrifugation electricity
Machine；20- filtering screens；The chassis 21-；22- solid-liquid mixing chambers；23- liquid storage chambers；24- balance rings.
Specific implementation mode
As shown in Figure 1, for a kind of heliotropin intermediate synthetic reaction post-processing method of the present invention, including walk as follows
Suddenly：
1) increase an auger 3 first at the discharge port 7 below 1 bottom valve of reaction kettle, the feed inlet 8 of auger 3 is made to be aligned
The discharge port 7 of reaction kettle 1, and it is smaller than 5cm between feed inlet 8 and discharge port 7, then it is arranged in the outlet end of auger 3
Elutriation kettle 2, elutriation kettle 2 are located at 10~20cm of lower section of the outlet end of auger 3, and auger 3 is made of acidproof material, Ke Yiyou
Effect prevents the concentrated sulfuric acid from causing to corrode to the inner wall and spiral conveyor rod 9 of auger 3, and then influences the normal work of auger 3, auger 3
It is equivalent to the pipeline reactor of a serialization, carries agitating function and heating function, by the temperature for adjusting rotating speed and hot water
Degree, can up regulation reaction speed to a certain degree, so that the reaction mixture material in 3 exit of arrival auger is just close to or up to instead
Terminal is answered, solves the problems, such as that the stirring of reaction later stage is difficult, piperonyl cyclonene and glyoxalic acid is enable smoothly to be realized for the technique of main material
Large-scale industrial production, while auger 3 is obliquely installed in the ゜ of 15 ゜~30, material can not only be reduced in transmission by being obliquely installed
Resistance, and liquid can be effectively prevent to be flowed out from feed inlet 8, improve safety, reduce 13 energy of driving motor
Loss；
2) glyoxalic acid is then added dropwise into reaction kettle 1, and is at the uniform velocity stirred with the speed of 40r/min, then according to the ratio 3:1
The pre-configured concentrated sulfuric acid is added dropwise, is cooled down with brine ice, and controls the nitration mixture temperature in reaction kettle 1 at 2~5 DEG C, 2
According to the ratio 2 in~4 hours:(1.5) required piperonyl cyclonene is added dropwise, and controls 35~40r/min of mixing speed；
3) start to be added dropwise and gradually generate solid product in reaction mixture after piperonyl cyclonene and gradually become viscous, when mixed liquor
Viscosity reaches 50~80mm2When/s, the bottom valve of reaction kettle 1 is opened, so that mixed liquor is passed through discharge port 7 and is discharged in auger 3, when
Start the driving motor 13 on auger 3, and adjust the rotating speed of driving motor 13 by frequency converter, while by the folder in the outside of auger 3
Set hot water inlet 6 and chuck hot water outlet 5 connect external water tank, and hot water is made to enter in chuck 4, and hot water heating is to accelerate
Reaction rate, early period, reaction all carried out at low temperature in reaction kettle 1, and reaction speed is partially slow, if into continuing to adopt after auger 3
Can be very long with the length of low-temp reaction, auger 3, it is improper, after material flows into auger 3, by 3 inside spin conveying lever 9 of auger
Stirring and chuck 4 in hot water heating, accelerate while moving ahead reaction, pass through the first temperature inductor inside auger 3
10, temperature difference (the first temperature inductor, the second temperature induction that second temperature inductor 11 and third temperature inductor 12 measure
Influence of the measuring temperature of device and third temperature inductor to reaction rate is as described in Table 1), spiral conveyor rod 9 is turned in real time
Speed and the temperature of hot water are adjusted, and reaction terminating when material being made to arrive at 3 outlet end of auger, three temperature inductors can be effective
Ground monitors the temperature inside auger, is controlled into trip temperature by the hot water in chuck, it is ensured that material can be in the stroke range of auger
It is interior that reaction was completed；
Influence of 1 temperature of table to reaction response rate
4) it leaves the material after auger 3 and is directly entered elutriation kettle 2, the water of 1000ml is previously added in elutriation kettle 2, works as material
It is diluted after, while terminating reaction, after all reaction masses enter elutriation kettle 2, continue to stir 15min, you can
Mixed solution is entered by vomit pipe 14 in centrifuge 15, the rotating speed of control centrifuge 15 is 300~500r/min, when centrifugation
Between 15min；
Centrifuge 15 is internally provided with centrifugal barrel (as shown in Figure 2), and centrifugal barrel divides centrifuge 15 for solid-liquid mixing chamber
22 and liquid storage chamber 23, centrifugal barrel include filtering screen 20 and chassis 21, filtering screen 20 is fixedly connected on the top on chassis 21
It is provided with pedestal 18 on face, below centrifugal barrel, centrifugation motor 19 is provided in pedestal 18, centrifugation motor 19 is connected by shaft
Chassis 21 is provided at least two balance rings 24 on the inner wall of centrifuge 15, drives centrifugal barrel rotation by centrifuging motor 19, makes
Mother liquor is detached with filter residue, improves 3,4- methylene-dioxy mandelic acid organic efficiencies, and balance ring 24 can make centrifugal barrel
Keep balance when rotated, prevent due to shake and influence the service life of centrifuge 15, balance ring 24 and filtering screen 20 it
Between spacing be 2~5mm, the gap of 2~5mm can reduce the frictional force between balance ring 24 and filtering screen 20, improve from
The rotary speed of heart bucket is provided with feed hopper 16 and escape pipe 17 on the top surface of centrifuge 15, and the material after the conveying of auger 3 is logical
Feed hopper 16 to be crossed to enter in centrifuge 15, escape pipe 17 can discharge the gas that generates when centrifugation, when improving centrifugation
Safety.
5) mother liquor after centrifugation is neutralized, and processing is dried in filter residue, obtains required reaction product 3,4-
Methylene-dioxy mandelic acid.
It these are only specific embodiments of the present invention, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, for the technique effect for realizing essentially identical, made ground simple change, equivalent replacement or modification etc. are all covered
Among protection scope of the present invention.
Claims (6)
1. a kind of heliotropin intermediate synthetic reaction post-processing method, it is characterised in that include the following steps：
1) discharge outlet first below reaction kettle bottom valve increases an auger, and the feed inlet of auger is made to be directed at going out for reaction kettle
Material mouth, and it is smaller than 5cm between the feed inlet and the discharge port, elutriation kettle then is set in the outlet end of auger,
The elutriation kettle is located at 10~20cm of lower section of the outlet end of the auger；
2) glyoxalic acid is then added dropwise into reaction kettle, and is at the uniform velocity stirred with the speed of 40r/min, then according to the ratio 3:1 is added dropwise
The pre-configured concentrated sulfuric acid, is cooled down with brine ice, and controls the nitration mixture temperature in reaction kettle at 2~5 DEG C, small 2~4
When interior according to the ratio 2:1.5 required piperonyl cyclonene is added dropwise；
3) start to be added dropwise and gradually generate solid product in reaction mixture after piperonyl cyclonene and gradually become viscous, it is sticky when mixed liquor
Degree reaches 50~80mm2When/s, the bottom valve of reaction kettle is opened, so that mixed liquor is passed through discharge port and is discharged in auger, starts auger
On driving motor, and adjust by frequency converter the rotating speed of driving motor, while by the chuck hot water inlet and folder on the outside of auger
The water tank outside hot water outlet connection is covered, hot water is made to enter in chuck, after material flows into auger, is conveyed by auger inside spin
The heating of hot water in the stirring of bar and chuck accelerates reaction while moving ahead, by the first temperature inductor inside auger,
The temperature difference that second temperature inductor and third temperature inductor measure, in real time to the temperature of the rotating speed of spiral conveyor rod and hot water
It is adjusted, reaction terminating when material being made to arrive at auger outlet end；
4) it leaves the material after auger and is directly entered the elutriation kettle, the water of 1000ml is previously added in the elutriation kettle, works as object
Material is diluted after entering, while terminating reaction, after all reaction masses enter the elutriation kettle, continues to stir 15min,
Mixed solution can be entered by vomit pipe in centrifuge, the rotating speed for controlling centrifuge is 300~500r/min, centrifugation time
15min；
5) mother liquor after centrifugation is neutralized, and processing is dried in filter residue, obtains required reaction product 3,4- methylenes
Two oxygroup mandelic acids.
2. a kind of heliotropin intermediate synthetic reaction post-processing method according to claim 1, it is characterised in that：Step
It is rapid 1) in the auger be made of acidproof material.
3. a kind of heliotropin intermediate synthetic reaction post-processing method according to claim 1, it is characterised in that：Step
It is rapid 1) in the auger be obliquely installed in the ゜ of 15 ゜~30.
4. a kind of heliotropin intermediate synthetic reaction post-processing method according to claim 1, it is characterised in that：Step
It is rapid 4) in the centrifuge be internally provided with centrifugal barrel, the centrifuge is divided into solid-liquid mixing chamber and liquid by the centrifugal barrel
Body storage chamber, the centrifugal barrel include filtering screen and chassis, and the filtering screen is fixedly connected on the top surface on the chassis,
It is provided with pedestal below the centrifugal barrel, centrifugation motor is provided in the pedestal, the centrifugation motor is connected by shaft
The chassis is provided at least two balance rings on the inner wall of the centrifuge.
5. a kind of heliotropin intermediate synthetic reaction post-processing method according to claim 4, it is characterised in that：Institute
It is 2~5mm to state the spacing between balance ring and the filtering screen.
6. a kind of heliotropin intermediate synthetic reaction post-processing method according to claim 4, it is characterised in that：Institute
It states and is provided with feed hopper and escape pipe on the top surface of centrifuge.
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| CN110684009B (en) * | 2018-07-04 | 2023-07-14 | 天津大学 | Method and device for synthesizing 3, 4-methylenedioxy-phenylglycolic acid by centrifugal extraction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379770A (en) * | 1999-10-13 | 2002-11-13 | 宇部兴产株式会社 | Process for preparation of 3,4-methylenedioxy-mandelic acid |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4186404B2 (en) * | 2000-10-04 | 2008-11-26 | 宇部興産株式会社 | Method for producing 3,4-methylenedioxymandelic acid |
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2016
- 2016-04-01 CN CN201610205663.6A patent/CN105777705B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1379770A (en) * | 1999-10-13 | 2002-11-13 | 宇部兴产株式会社 | Process for preparation of 3,4-methylenedioxy-mandelic acid |
| CN1400972A (en) * | 2000-02-02 | 2003-03-05 | 宇部兴产株式会社 | Process for preparing piperonal |
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Inventor after: Fan Bin Inventor after: Wang Guohong Inventor after: Liu Zhiming Inventor after: Huang Jingbo Inventor after: Lin Zhenhong Inventor after: Zhu Cicheng Inventor before: Yan Zhaochun |
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Effective date of registration: 20170421 Address after: Linjiang Town Nanping city Fujian province 353401 Pucheng County Garden No. 17 Applicant after: Fujian Renhong Medicine Chemical Industry Co., Ltd. Address before: Room 309, block C, building 6, No. 324000, triumph South Road, Zhejiang, Quzhou, China, 2 Applicant before: QUZHOU XINBU CHEMICAL TECHNOLOGY CO., LTD. |
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