CA2177939A1 - Process for the preparation of amino- and hydroxybenzonitriles - Google Patents
Process for the preparation of amino- and hydroxybenzonitrilesInfo
- Publication number
- CA2177939A1 CA2177939A1 CA 2177939 CA2177939A CA2177939A1 CA 2177939 A1 CA2177939 A1 CA 2177939A1 CA 2177939 CA2177939 CA 2177939 CA 2177939 A CA2177939 A CA 2177939A CA 2177939 A1 CA2177939 A1 CA 2177939A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- amino
- boron phosphate
- weight
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a process for the preparation of amino- or hydroxybenzonitriles of the general formula:
(I) in which X is an amino or hydroxyl group and the phenyl radical optionally carries additional alkyl substit-uents, by reaction of amino- or hydroxybenzoic acid derivatives of the general formula:
(II) in which R is a hydrogen atom or an alkyl radical containing up to 4 carbon atoms and the phenyl radical and X have the same meaning as above, with ammonia, wherein the reaction is carried out at a temperature of from 280 to 450°C in the presence of a boron phosphate carrier catalyst which is doped with trans-ition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of elements or with combinations thereof and the specific surface of which is at least 400 m2/g.
The present invention also provides boron phosphate carrier catalysts which are doped with one or more transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of elements and the specific surface of which is at least 400 m2/g.
With the use of the process and catalysts according to the present invention, amino- and hydroxybenzoic acids and the esters thereof can be selectively converted in high yields with high catalyst loading into amino- and hydroxybenzo-nitriles.
(I) in which X is an amino or hydroxyl group and the phenyl radical optionally carries additional alkyl substit-uents, by reaction of amino- or hydroxybenzoic acid derivatives of the general formula:
(II) in which R is a hydrogen atom or an alkyl radical containing up to 4 carbon atoms and the phenyl radical and X have the same meaning as above, with ammonia, wherein the reaction is carried out at a temperature of from 280 to 450°C in the presence of a boron phosphate carrier catalyst which is doped with trans-ition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of elements or with combinations thereof and the specific surface of which is at least 400 m2/g.
The present invention also provides boron phosphate carrier catalysts which are doped with one or more transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of elements and the specific surface of which is at least 400 m2/g.
With the use of the process and catalysts according to the present invention, amino- and hydroxybenzoic acids and the esters thereof can be selectively converted in high yields with high catalyst loading into amino- and hydroxybenzo-nitriles.
Description
Description The present iDvention is concerned with a proce~s for the prepsrstion of smino- a-nd h~dr~x~benzo-nitriIes of the. general formuls:
~ CN
x ~ (I) wherein ~ is an ~mino or h~drox~l group and the phen~l radical optionsll~ carrieæ further substituents..
There are numerous different proceæ~es for the prepa.rstion of aromatic Ditriles in which~ on 8 technicsl scale, the ammonoxidation of methglarenes is prefersbl~ carried out.
ID Kirk-Othmer, Enc~clopedia of Chemical ~echnolog~, Vol~ 15, p~ 904 et se~.. (1981), there i~ describe~ ~he s~nthesis of beDzonitrile and isophth~lonitrile-b~
D~ the smmonoxidation of toluene or m-x~lene, respect-ivel~.However, with this process it i~ not possible to convert, for-example, cresols.in an-economic msnner into h~drox~benzonitriles SiDC~ b~-products formed b~
oxidation irrever~sibl~ inactivste the catal~st after a short time.H~drox~benzonitriles which, inter slia, are importent intermediates for the. s~nthesis of pIant protection sgeDt~, are thus not obta~nsble technicall~ in this way~
For the preparation of h~drox~benzonitriles, there can be used, for ex~mple, the resction of h~rox~--21 77~3~
~3---benzoic scid esters with ammoDis.. Thus~ publi~hed Germsn Pa.tentApplication DE-OS 20 20 866 describes- a pro¢es~ iD which 4-h~droxybenzonitrile is prepared st an elevated tempersture from 4-h~drox~benzoic scid meth~l ester. As cst~l~st, there~is ~sed a phosphoric ~cid csrrierr cat~ t which iR
prepare~~ from phosphoric acid snd the carrier msterisl 5ilic8 gel with a specific surface srea of ~00 m /g snd which has a particle ~ize of 0..18 mm snd a content of phosphoric scid of 65~ A ~ield of 92%
is given for a contact time on the cstsl~st of 20 seconds. However, the low catal~st loading, which i8 8 measure for the efficienc~ and indicates what smount of the educt can be rescted per unit time-and the amount of ~he catalyæt, for example Mol h k~ 1, speaks against 8 lsr~e.-sc~le technical use of this proces~. A low cstsl~st loading sutomaticall~ leads to unsstisfactor~ space/time ~-ields snd thu~ to a poor ecoDo~ic efficienc~. ~urthermore, relstivel~-long hes tiDg-Up times of 20 to 30 hour~ are required for the production Qf the de~cribed cat~l~st.
In French Patent Specification ~R 2 332 261., there i8 also de~cribed the prepsration of 4-h~drox~-benzonitrile b~ the resction of a 4-h~drox~benzoic acid e~ter with ammonia in the gas ph~se.~ As catal~st~
there is u~ed boron phosphate which i8 Dot bound to a carrier aDd thus, becsu~e of the low resistance ~`` 21 77939 to attrition of the boron phosphste, is not ver~
suitable for use iD 8 fluidi~ed bed.
In compariæon with fixed bed resctions, fluidised bed proces~es have the sdvsntsge that the catal~6t tends much IeEs to caking and canal formation and, therefore, the service life of the cst~lgst iB
distinctl~ higher.~
As disadvsntsgeou~ in the csse of the process described in FR-PS 2 332 261 iB also be regarded the fact thst the reaction mixture of the 4-h~drox~-benzoic acid ester snd ammoDia i8 passed through a melt of the ester. Under these conditions, to a certsin extent there tskes place a conversion of the educt into phenol so that reduced yields result and 8 4-h~drox~benzonitrile is obtained which is contaminatedb~ considerable amount~ of phenol.
European Pstent EP O 074 116 is also concerned with the preparation of 4-h~drox~benzonitrile b~ the reaction of esters of 4-h~drox~benzoic acid with ammonia ~0 in the gas phase. As csrrier catal~ts, there sre~
thereb~ used not mQre closel~ defined silics but slso sluminium oxide, coating tsking place with boron phosphate. I-~ the ca~e of a contsct time of lQ seconds and s~reaction tempersture of 400C, ~ields of about 95~ ~re obtained. However, also in the case of this process, the cstalyst loading with 0.54 mmol of ester per grsm of cstal~t snd hour iB comp~rativel~ low.
`
The Soviet Patent Specification SU 1 007 717 discloses a specisl catal~t.which can be used for the preparstion of 4-hgdroxgbenzonitrile from esters of 4-hgdrox~benz~ic acid and ammonia. The tablet-formed catal~st is composed of boron (III) oxide,vsnadium (V) oxide and phosphorus (V) oxide which sre first added to an aqueous solution of starch psste, then granulated in 8 moist state, pressed and sub-sequentlg heated~ However~ satisfactorg flow rates cannot be achieved with the help of this catal~st.
Therefore, from the above-described disadvantages of the prior art, the.task has arisen to develop a.
process for the preparstion of amino- and hgdrox~-benzonitriles in which catal~sts are used which have a high abrasion resistance and can, in particular, be used also in fluidised bed processes. ~urthermore, the cartal~sts are to displag a high catsl~st loading in order that a high space/time ~ield can be achieved and the preparation of the saia nitriles can take place in an economic manner. In addition t these catalgsts are to be characterised bg a high select-ivit~..
~ his task is solved in that amino- or hydroxg-benzoic acid derivatives of the general formula:-~ COORx V lII) wherein R is a h~drogen atom or an alk~l radicsl containing up to 4 carbon atomæ and X is an amino or h~drox~l group and wherein the phen~l radicsl C8D
possibl~ also carrg additiona~ alk~l substituents, especiall~ Cl-C4-alk~l substituents are passed at a temperature of from 280 to 450C over a boron phosphate carrier catal~st which is doped with transitioD metal compouDds of the 5th, 6th, 12th or ~0 14th Group of the Periodic S~stem of Elements or with co~binations thereof and the specific surfsce thereof is at least 400 m2/g~
Surprisingl~ it has thereb.~ been shown th~t, besides amino- and h~drox~benzoic acid esters, amino-and h~d~rox~benzoic acids themselves can also be used,which, according to the previousl~ described processes, in which esters were exclusivel~ used as starting material, was not to have been expected.
In the case of the process according to the present invention, a doped boron ph~sphate carrier catsl~st is u~ed in which the proportion of the boron phosphate preferabl~ amounts to 0.01 to 15~ b~ weight and especiall~ to 0..5 to 5~ b~ weight, referred to the~
weight of the carrier material. With this catalgst, ~7~
there C8D be achieved a ~igh c8t81~st loading of ~ 1, and preferabl~ of ~ 2 mol of educt per kg of cstal~st and h.
According to 8 preferred embodiment of the process sccording to the present invention, a doped boron phosphste carrier cstsl~st is used which hss been produced iD such a manner that, in sn aqueous solution of O~OI to 15~ b~ weight and preferabl~ of 0.5 to ~%
b~ weight of phosphoric acid and 0.01 to 15~ b~ weight and prefersbl~ 0.1 to 3~ b~ weight of boric acid, there is dissolved 0.01 to 5% b~ weight and preferabl~
0~05 to 2% b~ weight of a sslt of the elements vans~ium~ niobium, tants~um, chromium, mol~bdenum, tungsten, csdmium, mercur~,- germaniumr tin, lead or ~5 zinc or of sng desired mixtures of these salts snd subsequentl~ stirred for 1 hour at ambient temperature.
Preferabl~, salts sre used which, as cstion, contain the respective elements and, as anion, ch~oride snd/or sulphste. However, it is re~dil~
Z0 possible th~t the salts contsin as anions the respective elements, for example vsnadstes, permanganates, mol~bdates or tungstates, and, a8 cations, preferablg ammonium ions.
~ubsequentl~, to this sslt solution are added 20 to 80~ b~ weight of 8 csrrier material which is preferabi~ selected from the group consisting of silicon dioxide, silics gel, sluminium oxide, zirconium oxide and titanium oxide or mixtures thereof and has a specific surfaGe of at lesEt 400 m2/g. The wster is subsequentl~ evaporated off, possibl~ under 8 vscuum, aDd, sccording to the present invention, the catsl~st is dried for a msximum of 3 hours at a temperature of from 100 to 500C with the paæsing over of a weak current of sir~ Dr~ing tempera.t ~ sof 150C hsve proved to be e~peciall~
suitable.
~ccording to the present invention,. the transitio~ metal-doped boron phosphate csrrier catal~st is chsrscterised b~ 8 surface which is ~400 m2/g and prefersbl~ ~ 500 m2/g. Ihis cstsl~st hss a preferred pore dismeter of 0~4 to 25 nm and ~5 especiall~ of 0.5 to 15 nm~
The sctusl r~action takes place, for exsmple, iD
a hestsble glsss tube with a frit insert which has a diameter of about 5 cm and is filled with 50 ml of the doped boron pho~phate carrier C8 tslgst. Ammoni~
preheated to 280 to 450QC is psssed through the r~ction tube and, st the same time, the desired reaction temperature is adjusted b~ means of an electronicsll~ regulated heating.
~he reaction temperature according to the present inveDtion i9 from 280 to 450C snd prefersbl~ from 300 to 420C~ Especisll~ good ~ields can be achieved iD the temperature: range of from 310 to 400C
21 77q39 ,. ~
_9_ A~ amino- and hydrox~benzoic acid derivatives, in the scope of the present invention there are to be understood not onl~ the acids but also the esters thereof which, after resching the desired resction ~ 5 temperature, are introduced continuouslg in liquid or dissolved form into the gas Ftream snd evaporated. In the last-mentioned case, use can be made of inert solvents, fQr example aliphatic and sromstic h~dro-carbonæ, ethers or nitriIes. TolueDe, benzene snd benzonitrile have provéd to be e~pecisll~ suitsble.
A solution or melt of the amino- or h~droxgbenzoic scid or of the corresponding ester is do~ed into the ammonia stream below the frit and thereb~ evaporated.
~he gas stream then passes through the fluidised bed from below upwardl~. The diameter of the spheroidal catalyst particle~ should thereb~ be from 0.2 to 2 mm.
I" a following separator, the product is condensed and the ammonia can be rec~cled and/or recovered. Inert gases, for example nitrogen,;are not necessar~ in this c~clic process but can be used.
If the process accordi~g to the present invention is to be carried out in a fixed bed, then it is recommended to use catal~st formed bodies with a diameter of from 2.0 to 8.0 mm.
~ith the help of the process according to the present iDvention, there can be achieved gield~ and selectivities of up to 100% and catal~st loadings of `~
--1 o up to 5 mol of ~tarting material per kg o~ catal~st and hour.
A further subject of the present invention is a boron phoephate carrier catal~st which is doped with one or more transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic Sgstem of the elements and the specific surface area of which is at least 400 m2/g. ThiS catal~st can be used for the preparation of aromatic amino- or h~drox~- substituted nitriles b~ the reaction of aromstic amino- or h~drox~-substituted csrbox~lic acids or carbox~lic acid esters with ammonia.
~ he following Examples are given for the purpose of illustrsting the present invention.
I5 Example~.
Productl~ of the catal~st.
~xample l.
5.~88 g of an 85~ orthophosphoric acid and 3.33 g of a 99.~8~ boric acid are dissolved in 500 g of distilled water. After 3.6 g zinc sulphate have additionall~ been dis~olved therein, stirring is carried out for 1 hour at ~mbient temperature.
Subsequentl~ 500 g silica gel are added thereto, the surface area of which is ~4Q0 m2/g and which has a pore di~ameter of from 0 4 to 25 nm. Evaporation ~o dr~nes~ is subsequentl~ carried out at 60C under reduced pressure and then heated for 3 hours to 150C with the psssing over of a weak stream of air.
After-cooling, the carrier cstalgst so obtained can be used in the described manner.
The catal~sts of the following Examples 2 to 5 were produced analogousl~ to ~xample 1. Instesd of 3.6 g of zinc sulphste, doping wa~ carriea out with the following compounds:
Examp~e 2: 3.2 g ammonium pertungstate E~smple 3: 2.8 g tin chloride E~ample 4: 0.6 g ammonium metavsnadste~
Examp~e 5: 1~4 g tin chloride + 1.6 g smmonium pertung~tate.
Proce~s examples.
E~ample~ 6.
A`heat~ble glas~ tube (dismeter 5 cm) with a frit bottom i8 filled with 50 ml of the zinc-doped boron phQsphate carrier catsl~st produced sccording to Example 1, Through the reaction tube i~ psssed smmQnia prehested to 340C snd, st the same time, a resction 2~ temperature of 34QC is sdjusted b~ mesns of electronicsll~-re~ulated hes-ting. As soon as this is resched, 200 mmol 4-h~drox~beDzoic scid meth~l e~ter (4-~BSME)- are dosed into the gas stresm below the frit with a speed of 50 mmol/h. ~he emerging gs~
stresm is cooled in 8 separator, the resction product thereb~ separating out. In this W8~ ,; 4-h~drox~benzo-nitrile i~ obtsined in 95~ ~ield. As b~-product, _l ?--0~6~ of phenol can be detected. ~he æelectivitg is 99% and the catal~st loading is 2 mol~kg l-h 1~
In the following Examples set out in the Tsble, the procedure corresponds to that of Example 6~
o ~
~ O O C`J r l P~
O
a) N
P~
rl CS~ ~ ~ h O u~ ~ m ~ o I O~ o ~C)I r r1 -rl ~ r l o ~D
I ~1 ,Q r ~ ~ O O ~ O
~ o o ~ m ~ ~
r, ~ p: ~ r l t~
a U: O O CU o ~
~ ~ o ~ ~ m ~ o ~ o a rl H
I ~ ~ O O C~ O
o U~ ~ m ~
~ 0~ 1 ,n ~ O O ~ O
r-- Ir o o r-~ T O ~~
o ~;
O O C~J O ~ ~ O
~x ~ o ~ ~ m ~ o ~_ m - ~ h ,I m ~ ~ r~ ~ P
r~ O r~ ~ ~
f o ~ I r ~ ~ ~ ~ O
r-l ~ ~ ~ c~ ~ ~ ~ a o O ~ ~ ~ o ~ o ~1 ~1 O ~ O ~D a) ~ P, ~
-~D ~ ~ a Ir o o c~ ~ h o ~ o ~ cn ~-- h O C-r ~ ~l t ,~,Q
O '~
N ~ O O C~l o ~ O O C~l O
--~ 2 ~ P~ ~ ~
,~
~ o o c~ n o O ~ o u~ ~ m o o ~ te o c~ O ~ 0 cn ~d O N
O 'C 00 t ~ 5:1 Y ~ . ~ ~ v ,~ oV .l, ~æ P
o o ~ u u u td td ~ O ~ Oq O d ~ ~ ~ rJ
~ q ~ E~ rl v ~ r~ u ~ C~
~ CN
x ~ (I) wherein ~ is an ~mino or h~drox~l group and the phen~l radical optionsll~ carrieæ further substituents..
There are numerous different proceæ~es for the prepa.rstion of aromatic Ditriles in which~ on 8 technicsl scale, the ammonoxidation of methglarenes is prefersbl~ carried out.
ID Kirk-Othmer, Enc~clopedia of Chemical ~echnolog~, Vol~ 15, p~ 904 et se~.. (1981), there i~ describe~ ~he s~nthesis of beDzonitrile and isophth~lonitrile-b~
D~ the smmonoxidation of toluene or m-x~lene, respect-ivel~.However, with this process it i~ not possible to convert, for-example, cresols.in an-economic msnner into h~drox~benzonitriles SiDC~ b~-products formed b~
oxidation irrever~sibl~ inactivste the catal~st after a short time.H~drox~benzonitriles which, inter slia, are importent intermediates for the. s~nthesis of pIant protection sgeDt~, are thus not obta~nsble technicall~ in this way~
For the preparation of h~drox~benzonitriles, there can be used, for ex~mple, the resction of h~rox~--21 77~3~
~3---benzoic scid esters with ammoDis.. Thus~ publi~hed Germsn Pa.tentApplication DE-OS 20 20 866 describes- a pro¢es~ iD which 4-h~droxybenzonitrile is prepared st an elevated tempersture from 4-h~drox~benzoic scid meth~l ester. As cst~l~st, there~is ~sed a phosphoric ~cid csrrierr cat~ t which iR
prepare~~ from phosphoric acid snd the carrier msterisl 5ilic8 gel with a specific surface srea of ~00 m /g snd which has a particle ~ize of 0..18 mm snd a content of phosphoric scid of 65~ A ~ield of 92%
is given for a contact time on the cstsl~st of 20 seconds. However, the low catal~st loading, which i8 8 measure for the efficienc~ and indicates what smount of the educt can be rescted per unit time-and the amount of ~he catalyæt, for example Mol h k~ 1, speaks against 8 lsr~e.-sc~le technical use of this proces~. A low cstsl~st loading sutomaticall~ leads to unsstisfactor~ space/time ~-ields snd thu~ to a poor ecoDo~ic efficienc~. ~urthermore, relstivel~-long hes tiDg-Up times of 20 to 30 hour~ are required for the production Qf the de~cribed cat~l~st.
In French Patent Specification ~R 2 332 261., there i8 also de~cribed the prepsration of 4-h~drox~-benzonitrile b~ the resction of a 4-h~drox~benzoic acid e~ter with ammonia in the gas ph~se.~ As catal~st~
there is u~ed boron phosphate which i8 Dot bound to a carrier aDd thus, becsu~e of the low resistance ~`` 21 77939 to attrition of the boron phosphste, is not ver~
suitable for use iD 8 fluidi~ed bed.
In compariæon with fixed bed resctions, fluidised bed proces~es have the sdvsntsge that the catal~6t tends much IeEs to caking and canal formation and, therefore, the service life of the cst~lgst iB
distinctl~ higher.~
As disadvsntsgeou~ in the csse of the process described in FR-PS 2 332 261 iB also be regarded the fact thst the reaction mixture of the 4-h~drox~-benzoic acid ester snd ammoDia i8 passed through a melt of the ester. Under these conditions, to a certsin extent there tskes place a conversion of the educt into phenol so that reduced yields result and 8 4-h~drox~benzonitrile is obtained which is contaminatedb~ considerable amount~ of phenol.
European Pstent EP O 074 116 is also concerned with the preparation of 4-h~drox~benzonitrile b~ the reaction of esters of 4-h~drox~benzoic acid with ammonia ~0 in the gas phase. As csrrier catal~ts, there sre~
thereb~ used not mQre closel~ defined silics but slso sluminium oxide, coating tsking place with boron phosphate. I-~ the ca~e of a contsct time of lQ seconds and s~reaction tempersture of 400C, ~ields of about 95~ ~re obtained. However, also in the case of this process, the cstalyst loading with 0.54 mmol of ester per grsm of cstal~t snd hour iB comp~rativel~ low.
`
The Soviet Patent Specification SU 1 007 717 discloses a specisl catal~t.which can be used for the preparstion of 4-hgdroxgbenzonitrile from esters of 4-hgdrox~benz~ic acid and ammonia. The tablet-formed catal~st is composed of boron (III) oxide,vsnadium (V) oxide and phosphorus (V) oxide which sre first added to an aqueous solution of starch psste, then granulated in 8 moist state, pressed and sub-sequentlg heated~ However~ satisfactorg flow rates cannot be achieved with the help of this catal~st.
Therefore, from the above-described disadvantages of the prior art, the.task has arisen to develop a.
process for the preparstion of amino- and hgdrox~-benzonitriles in which catal~sts are used which have a high abrasion resistance and can, in particular, be used also in fluidised bed processes. ~urthermore, the cartal~sts are to displag a high catsl~st loading in order that a high space/time ~ield can be achieved and the preparation of the saia nitriles can take place in an economic manner. In addition t these catalgsts are to be characterised bg a high select-ivit~..
~ his task is solved in that amino- or hydroxg-benzoic acid derivatives of the general formula:-~ COORx V lII) wherein R is a h~drogen atom or an alk~l radicsl containing up to 4 carbon atomæ and X is an amino or h~drox~l group and wherein the phen~l radicsl C8D
possibl~ also carrg additiona~ alk~l substituents, especiall~ Cl-C4-alk~l substituents are passed at a temperature of from 280 to 450C over a boron phosphate carrier catal~st which is doped with transitioD metal compouDds of the 5th, 6th, 12th or ~0 14th Group of the Periodic S~stem of Elements or with co~binations thereof and the specific surfsce thereof is at least 400 m2/g~
Surprisingl~ it has thereb.~ been shown th~t, besides amino- and h~drox~benzoic acid esters, amino-and h~d~rox~benzoic acids themselves can also be used,which, according to the previousl~ described processes, in which esters were exclusivel~ used as starting material, was not to have been expected.
In the case of the process according to the present invention, a doped boron ph~sphate carrier catsl~st is u~ed in which the proportion of the boron phosphate preferabl~ amounts to 0.01 to 15~ b~ weight and especiall~ to 0..5 to 5~ b~ weight, referred to the~
weight of the carrier material. With this catalgst, ~7~
there C8D be achieved a ~igh c8t81~st loading of ~ 1, and preferabl~ of ~ 2 mol of educt per kg of cstal~st and h.
According to 8 preferred embodiment of the process sccording to the present invention, a doped boron phosphste carrier cstsl~st is used which hss been produced iD such a manner that, in sn aqueous solution of O~OI to 15~ b~ weight and preferabl~ of 0.5 to ~%
b~ weight of phosphoric acid and 0.01 to 15~ b~ weight and prefersbl~ 0.1 to 3~ b~ weight of boric acid, there is dissolved 0.01 to 5% b~ weight and preferabl~
0~05 to 2% b~ weight of a sslt of the elements vans~ium~ niobium, tants~um, chromium, mol~bdenum, tungsten, csdmium, mercur~,- germaniumr tin, lead or ~5 zinc or of sng desired mixtures of these salts snd subsequentl~ stirred for 1 hour at ambient temperature.
Preferabl~, salts sre used which, as cstion, contain the respective elements and, as anion, ch~oride snd/or sulphste. However, it is re~dil~
Z0 possible th~t the salts contsin as anions the respective elements, for example vsnadstes, permanganates, mol~bdates or tungstates, and, a8 cations, preferablg ammonium ions.
~ubsequentl~, to this sslt solution are added 20 to 80~ b~ weight of 8 csrrier material which is preferabi~ selected from the group consisting of silicon dioxide, silics gel, sluminium oxide, zirconium oxide and titanium oxide or mixtures thereof and has a specific surfaGe of at lesEt 400 m2/g. The wster is subsequentl~ evaporated off, possibl~ under 8 vscuum, aDd, sccording to the present invention, the catsl~st is dried for a msximum of 3 hours at a temperature of from 100 to 500C with the paæsing over of a weak current of sir~ Dr~ing tempera.t ~ sof 150C hsve proved to be e~peciall~
suitable.
~ccording to the present invention,. the transitio~ metal-doped boron phosphate csrrier catal~st is chsrscterised b~ 8 surface which is ~400 m2/g and prefersbl~ ~ 500 m2/g. Ihis cstsl~st hss a preferred pore dismeter of 0~4 to 25 nm and ~5 especiall~ of 0.5 to 15 nm~
The sctusl r~action takes place, for exsmple, iD
a hestsble glsss tube with a frit insert which has a diameter of about 5 cm and is filled with 50 ml of the doped boron pho~phate carrier C8 tslgst. Ammoni~
preheated to 280 to 450QC is psssed through the r~ction tube and, st the same time, the desired reaction temperature is adjusted b~ means of an electronicsll~ regulated heating.
~he reaction temperature according to the present inveDtion i9 from 280 to 450C snd prefersbl~ from 300 to 420C~ Especisll~ good ~ields can be achieved iD the temperature: range of from 310 to 400C
21 77q39 ,. ~
_9_ A~ amino- and hydrox~benzoic acid derivatives, in the scope of the present invention there are to be understood not onl~ the acids but also the esters thereof which, after resching the desired resction ~ 5 temperature, are introduced continuouslg in liquid or dissolved form into the gas Ftream snd evaporated. In the last-mentioned case, use can be made of inert solvents, fQr example aliphatic and sromstic h~dro-carbonæ, ethers or nitriIes. TolueDe, benzene snd benzonitrile have provéd to be e~pecisll~ suitsble.
A solution or melt of the amino- or h~droxgbenzoic scid or of the corresponding ester is do~ed into the ammonia stream below the frit and thereb~ evaporated.
~he gas stream then passes through the fluidised bed from below upwardl~. The diameter of the spheroidal catalyst particle~ should thereb~ be from 0.2 to 2 mm.
I" a following separator, the product is condensed and the ammonia can be rec~cled and/or recovered. Inert gases, for example nitrogen,;are not necessar~ in this c~clic process but can be used.
If the process accordi~g to the present invention is to be carried out in a fixed bed, then it is recommended to use catal~st formed bodies with a diameter of from 2.0 to 8.0 mm.
~ith the help of the process according to the present iDvention, there can be achieved gield~ and selectivities of up to 100% and catal~st loadings of `~
--1 o up to 5 mol of ~tarting material per kg o~ catal~st and hour.
A further subject of the present invention is a boron phoephate carrier catal~st which is doped with one or more transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic Sgstem of the elements and the specific surface area of which is at least 400 m2/g. ThiS catal~st can be used for the preparation of aromatic amino- or h~drox~- substituted nitriles b~ the reaction of aromstic amino- or h~drox~-substituted csrbox~lic acids or carbox~lic acid esters with ammonia.
~ he following Examples are given for the purpose of illustrsting the present invention.
I5 Example~.
Productl~ of the catal~st.
~xample l.
5.~88 g of an 85~ orthophosphoric acid and 3.33 g of a 99.~8~ boric acid are dissolved in 500 g of distilled water. After 3.6 g zinc sulphate have additionall~ been dis~olved therein, stirring is carried out for 1 hour at ~mbient temperature.
Subsequentl~ 500 g silica gel are added thereto, the surface area of which is ~4Q0 m2/g and which has a pore di~ameter of from 0 4 to 25 nm. Evaporation ~o dr~nes~ is subsequentl~ carried out at 60C under reduced pressure and then heated for 3 hours to 150C with the psssing over of a weak stream of air.
After-cooling, the carrier cstalgst so obtained can be used in the described manner.
The catal~sts of the following Examples 2 to 5 were produced analogousl~ to ~xample 1. Instesd of 3.6 g of zinc sulphste, doping wa~ carriea out with the following compounds:
Examp~e 2: 3.2 g ammonium pertungstate E~smple 3: 2.8 g tin chloride E~ample 4: 0.6 g ammonium metavsnadste~
Examp~e 5: 1~4 g tin chloride + 1.6 g smmonium pertung~tate.
Proce~s examples.
E~ample~ 6.
A`heat~ble glas~ tube (dismeter 5 cm) with a frit bottom i8 filled with 50 ml of the zinc-doped boron phQsphate carrier catsl~st produced sccording to Example 1, Through the reaction tube i~ psssed smmQnia prehested to 340C snd, st the same time, a resction 2~ temperature of 34QC is sdjusted b~ mesns of electronicsll~-re~ulated hes-ting. As soon as this is resched, 200 mmol 4-h~drox~beDzoic scid meth~l e~ter (4-~BSME)- are dosed into the gas stresm below the frit with a speed of 50 mmol/h. ~he emerging gs~
stresm is cooled in 8 separator, the resction product thereb~ separating out. In this W8~ ,; 4-h~drox~benzo-nitrile i~ obtsined in 95~ ~ield. As b~-product, _l ?--0~6~ of phenol can be detected. ~he æelectivitg is 99% and the catal~st loading is 2 mol~kg l-h 1~
In the following Examples set out in the Tsble, the procedure corresponds to that of Example 6~
o ~
~ O O C`J r l P~
O
a) N
P~
rl CS~ ~ ~ h O u~ ~ m ~ o I O~ o ~C)I r r1 -rl ~ r l o ~D
I ~1 ,Q r ~ ~ O O ~ O
~ o o ~ m ~ ~
r, ~ p: ~ r l t~
a U: O O CU o ~
~ ~ o ~ ~ m ~ o ~ o a rl H
I ~ ~ O O C~ O
o U~ ~ m ~
~ 0~ 1 ,n ~ O O ~ O
r-- Ir o o r-~ T O ~~
o ~;
O O C~J O ~ ~ O
~x ~ o ~ ~ m ~ o ~_ m - ~ h ,I m ~ ~ r~ ~ P
r~ O r~ ~ ~
f o ~ I r ~ ~ ~ ~ O
r-l ~ ~ ~ c~ ~ ~ ~ a o O ~ ~ ~ o ~ o ~1 ~1 O ~ O ~D a) ~ P, ~
-~D ~ ~ a Ir o o c~ ~ h o ~ o ~ cn ~-- h O C-r ~ ~l t ,~,Q
O '~
N ~ O O C~l o ~ O O C~l O
--~ 2 ~ P~ ~ ~
,~
~ o o c~ n o O ~ o u~ ~ m o o ~ te o c~ O ~ 0 cn ~d O N
O 'C 00 t ~ 5:1 Y ~ . ~ ~ v ,~ oV .l, ~æ P
o o ~ u u u td td ~ O ~ Oq O d ~ ~ ~ rJ
~ q ~ E~ rl v ~ r~ u ~ C~
Claims (17)
1. Process for the preparation of amino- or hydroxy-benzonitriles of the general formula:
(I) wherein X is an amino or hydroxyl group and the phenyl radical optionally carries additional alkyl substit-uents, by the reaction of amino- or hydroxybenzoic acid derivatives of the general formula:
(II) wherein R is a hydrogen atom or an alkyl radical containing up to 4 carbon atoms and the phenyl radical and X have the same meanings as above, with ammonia, wherein the reaction is carried out at a temperature of from 280 to 450°C in the presence of a boron phosphate carrier catalyst which is doped with transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of the elements or with combinations thereof and the specific surface of which is at least 400 m2/g.
(I) wherein X is an amino or hydroxyl group and the phenyl radical optionally carries additional alkyl substit-uents, by the reaction of amino- or hydroxybenzoic acid derivatives of the general formula:
(II) wherein R is a hydrogen atom or an alkyl radical containing up to 4 carbon atoms and the phenyl radical and X have the same meanings as above, with ammonia, wherein the reaction is carried out at a temperature of from 280 to 450°C in the presence of a boron phosphate carrier catalyst which is doped with transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of the elements or with combinations thereof and the specific surface of which is at least 400 m2/g.
2. Process according to claim 1, wherein the amount of boron phosphate is 0.01 to 15% by weight, referred to the weight of the carrier material.
3. Process according to claim 2, wherein the amount of boron phosphate is 0.5 to 5% by weight, referred to the weight of the carrier material.
4. Process according to any of the preceding claims, wherein a boron phosphate carrier catalyst is used which has been produced by treating the carrier material with aqueous solutions of 0.01 to 15% by weight of phosphoric acid, 0.01 to 15% by weight of boric acid and 0.01 to 5% by weight of salts of transition metals of the 5th, 6th, 12th or 14th Group of the Periodic System of elements or combinations of such salts.
5. Process according to any of the preceding claims, wherein the carrier material is selected from the group consisting of silicon dioxide, silica gel, aluminium oxide, titanium oxide or zirconium oxide or mixtures thereof.
6. Process according to any of the preceding claims, wherein, as transition metal compounds, there are used salts of the elements vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cadmium, mercury, germanium, tin, lead or zinc or combinations of these salts.
7. Process according to claim 6, wherein the salts contain as cation the respective element and, as anion, chloride and/or sulphate.
8. Process according to claim 6, wherein the salts contain as anion the respective element and ammonium as cation.
9. Process according to any of the preceding claims, wherein the specific surface of the doped boron phosphate carrier catalyst is > 500 m2/g.
10. Process according to any of the preceding claims, wherein the doped boron phosphate carrier catalyst has a pore diameter of from 0.4 to 25 nm.
11, Process according to claim 10, wherein the doped boron phosphate carrier catalyst has a pore diameter of 0.5 to 15 nm.
12. Process according to any of the preceding claims, wherein the doped boron phosphate carrier catalyst has been dried for up to 3 hours at a temperature of from 100 to 500°C.
13. Process according to any of the preceding claims, wherein the amino- or hydroxybenzoic acid derivative is used in liquid or in dissolved form.
14. Process according to any of the preceding claims, wherein the benzoic acid derivative is reacted at a temperature of from 300 to 420°C.
15. Process according to any of the preceding claims, wherein unreacted ammonia is recycled and/or recovered.
16. Boron phosphate carrier catalyst which is doped with one or more transition metal compounds of the 5th, 6th, 12th or 14th Group of the Periodic System of elements and the specific surface of which is at least 400 m2/g.
17. Use of boron phosphate carrier catalysts according to claim 16 for the preparation of aromatic amino- or hydroxy-substituted nitriles by the reaction of aromatic amino- or hydroxy-substituted carboxylic acids or carboxylic acid esters with ammonia.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19520491.3 | 1995-06-03 | ||
| DE1995120491 DE19520491A1 (en) | 1995-06-03 | 1995-06-03 | Process for the preparation of amino and hydroxybenzonitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2177939A1 true CA2177939A1 (en) | 1996-12-04 |
Family
ID=7763660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2177939 Abandoned CA2177939A1 (en) | 1995-06-03 | 1996-05-31 | Process for the preparation of amino- and hydroxybenzonitriles |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0745585A1 (en) |
| JP (1) | JPH08333321A (en) |
| CN (1) | CN1146452A (en) |
| CA (1) | CA2177939A1 (en) |
| CZ (1) | CZ153696A3 (en) |
| DE (1) | DE19520491A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005054362A1 (en) | 2004-12-01 | 2006-06-08 | Degussa Ag | Process for the preparation of amino or hydroxybenzonitriles |
| CN103864644B (en) * | 2014-04-04 | 2016-06-08 | 武汉大学 | A kind of method preparing cyanobenzene by phenylformic acid gas phase ammonification |
| CN106140234B (en) * | 2015-04-17 | 2019-04-05 | 中国石油天然气股份有限公司 | Solid phosphoric acid catalyst and preparation method thereof for producing adiponitrile |
| CN106699601B (en) * | 2015-11-12 | 2019-01-01 | 中触媒新材料股份有限公司 | One-step method for synthesizing of the one kind to (neighbour) hydroxy-phenylformonitrile |
| CN105418455A (en) * | 2015-12-23 | 2016-03-23 | 江苏瑞达环保科技有限公司 | Method for preparing p-hydroxybenzonitrile |
| CN108816256B (en) * | 2018-06-06 | 2021-04-23 | 辽宁格瑞凯特科技有限公司 | Preparation method of catalyst for synthesizing salicylaldehyde |
| CN112705232B (en) * | 2019-10-24 | 2023-06-06 | 南通泰禾化工股份有限公司 | Catalyst for preparing salicylonitrile and preparation method and application thereof |
| CN110698362A (en) * | 2019-10-30 | 2020-01-17 | 泰州百力化学股份有限公司 | Process for synthesizing salicylonitrile by continuous method |
| CN111138318B (en) * | 2020-01-17 | 2023-02-03 | 盐城工学院 | Method for preparing p-hydroxybenzonitrile by using methyl p-hydroxybenzoate and urea |
| CN111138317B (en) * | 2020-01-17 | 2023-02-03 | 盐城工学院 | Method for preparing o-hydroxybenzonitrile by using methyl salicylate and urea |
| CN112457213B (en) * | 2020-08-28 | 2022-08-30 | 鞍山七彩化学股份有限公司 | Catalytic synthesis method of p-aminobenzonitrile |
| CN112645840B (en) * | 2021-01-22 | 2022-04-22 | 常州大学 | Method for preparing salicylamide by salicylamide continuous method |
| CN114181111A (en) * | 2021-12-09 | 2022-03-15 | 江阴苏利化学股份有限公司 | Synthesis method of m- (p) -alkyl substituted benzonitrile |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB535187A (en) * | 1938-09-30 | 1941-04-01 | Du Pont | Improvements in or relating to the manufacture of nitriles |
| US2200734A (en) * | 1938-09-30 | 1940-05-14 | Du Pont | Manufacture of nitriles |
| DE857048C (en) * | 1941-03-19 | 1952-11-27 | Basf Ag | Process for the catalytic production of carboxylic acid dinitriles |
| US3393222A (en) * | 1964-07-23 | 1968-07-16 | Bayer Ag | Process for the production of nitriles |
| DE1279020B (en) * | 1966-08-04 | 1968-10-03 | Hoechst Ag | Process for the continuous production of aliphatic or aromatic nitriles from carboxylic acid esters |
| DE2020866A1 (en) * | 1970-04-29 | 1971-11-18 | Basf Ag | Hydroxy- and aminobenzonitriles prepd from benzoates using silica - gel soaked with phos |
| FR2332261A1 (en) * | 1975-11-21 | 1977-06-17 | Rhone Poulenc Ind | Prepn. of hydroxy benzonitriles - by passage of ammonia and an alkyl hydroxy benzoate over boron phosphate catalyst |
| SU1007717A1 (en) * | 1981-02-06 | 1983-03-30 | Ордена Трудового Красного Знамени Институт Химических Наук Ан Казсср | Catalyst for ammonolysis of n-oxybenzoates |
| DE3131968A1 (en) * | 1981-08-13 | 1983-02-24 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR PRODUCING ALIPHATIC NITRILES |
| JPS5841852A (en) * | 1981-09-07 | 1983-03-11 | Ueno Seiyaku Oyo Kenkyusho:Kk | Preparation of oxybenzonitriles |
| DE3510876A1 (en) * | 1985-03-26 | 1986-10-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING ALIPHATIC DINITRILE |
| FR2617412B1 (en) * | 1987-07-01 | 1993-05-14 | Inst Francais Du Petrole | CATALYST COMPRISING A MINERAL SUPPORT, PHOSPHORUS AND BORON, METHODS OF PREPARATION AND USE IN HYDROREFINING OF OIL CUTS |
| DE3923979A1 (en) * | 1989-07-20 | 1991-01-24 | Merck Patent Gmbh | METHOD FOR PRODUCING AROMATIC NITRILES |
-
1995
- 1995-06-03 DE DE1995120491 patent/DE19520491A1/en not_active Withdrawn
-
1996
- 1996-05-24 JP JP8130369A patent/JPH08333321A/en active Pending
- 1996-05-28 CZ CZ961536A patent/CZ153696A3/en unknown
- 1996-05-31 EP EP96108783A patent/EP0745585A1/en not_active Withdrawn
- 1996-05-31 CA CA 2177939 patent/CA2177939A1/en not_active Abandoned
- 1996-05-31 CN CN 96110493 patent/CN1146452A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08333321A (en) | 1996-12-17 |
| CN1146452A (en) | 1997-04-02 |
| DE19520491A1 (en) | 1996-12-05 |
| CZ153696A3 (en) | 1997-01-15 |
| EP0745585A1 (en) | 1996-12-04 |
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