CA1039740A - Process for the preparation of aromatic carbonates - Google Patents
Process for the preparation of aromatic carbonatesInfo
- Publication number
- CA1039740A CA1039740A CA229,892A CA229892A CA1039740A CA 1039740 A CA1039740 A CA 1039740A CA 229892 A CA229892 A CA 229892A CA 1039740 A CA1039740 A CA 1039740A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- process according
- carbonate
- phenol
- reaction
- 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.)
- Expired
Links
- -1 aromatic carbonates Chemical class 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 150000007860 aryl ester derivatives Chemical class 0.000 claims abstract 2
- 125000004122 cyclic group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims 1
- 150000007517 lewis acids Chemical class 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 150000003623 transition metal compounds Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 229920000515 polycarbonate Polymers 0.000 abstract description 2
- 239000004417 polycarbonate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- BSFODEXXVBBYOC-UHFFFAOYSA-N 8-[4-(dimethylamino)butan-2-ylamino]quinolin-6-ol Chemical compound C1=CN=C2C(NC(CCN(C)C)C)=CC(O)=CC2=C1 BSFODEXXVBBYOC-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002844 continuous effect Effects 0.000 description 2
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 241001527806 Iti Species 0.000 description 1
- 241001163743 Perlodes Species 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229910008046 SnC14 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010061 TiC13 Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- ACBQROXDOHKANW-UHFFFAOYSA-N bis(4-nitrophenyl) carbonate Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC(=O)OC1=CC=C([N+]([O-])=O)C=C1 ACBQROXDOHKANW-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-WFGJKAKNSA-N bis(trideuteriomethyl) carbonate Chemical compound [2H]C([2H])([2H])OC(=O)OC([2H])([2H])[2H] IEJIGPNLZYLLBP-WFGJKAKNSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LRMHFDNWKCSEQU-UHFFFAOYSA-N ethoxyethane;phenol Chemical compound CCOCC.OC1=CC=CC=C1 LRMHFDNWKCSEQU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HPICRATUQFHULE-UHFFFAOYSA-J uranium(4+);tetrachloride Chemical compound Cl[U](Cl)(Cl)Cl HPICRATUQFHULE-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE Aromatic carbonates having the general formula: (I) wherein R is an alkyl, alkoxy, aryl or aryloxy radical or a nitro group and R1 is an alkyl group or a radical of the formula: in which R has the aforesaid meaning, are prepared by reacting corresponding phenols or aryl esters thereof with alkyl, cyclic or aryl-alkyl carbonates, in the presence of a catalyst. The aromatic carbonates of formula (I) serve as intermediates in the production of aromatic polycarbonates and in the synthesis of various isocyanates.
Description
~)39740 ~ he present invention i~ concerned ~ith a process for the preparation of aromatic carbonate~ having the general formula:
O
~ O_C_OR' (1-5) wherein R i9 an alkyl, alkoxy, aryl or aryloxy radicsl or a nitro group and Rl is an alkyl group or a radical of the formula:
~ : '.
(1-5) ' ' in which R has the nforesaid meanings.
M~thod~ for the preparation of these compounds are known~
starting from the corresponding phenols through a reaotion with phosgene or chloroformiates according to complex technologies.
These however, present several risks due to the toxioity of the reagents employed and give rise to the formation of hydrochloric aoid 8~ by-product. ~ ;
On the other hand, it i~ also known to react phenols and alkyl carbonates in preeence of ~trong ba~es aa oataly~t, Such a reaotion ha~ however the drawbaok of lo~ reaotion rate~ and the ~ormation of high amounts of phenol ether as by-products.
Aromatio carbonates ha~e a remarkable industrial applica-t~on ~ince they can be employed as intermediates in the produ¢tion ~ . .
;~ Or aromatic polyoarbonates and in the synthesi~ of various isocy-.
anate~.
It has no~ been found that it is possible to obtain, at . ~
~ hi p yields and selectivities, aryl-alkyl carbonates and diaryl : : , carbonates according to the present in~ention, these are obtained by reacting the corresponding phenQls or acyl esters thereof with ;alkyl cyclic or aryl-alkyl carbonates, in the presence of suitable ~catalys~t~ he reaction i9 carried out in the liquid pha~e, ~ith ,;; ,.'.'. ;:,, ,~', ~"; ',"',''";."."'' ;
~)39740 - ~
or without a solvent, at a temperature of from 25 to 350C, pre-ferably from 80 to 250~, and 8 pressure of from 0.1 to 100 atm "
pre~erably from 1 to 25 atm.
The molar ratio between the phenol and carbonate com-pounds may range from 100:1 to 1:100, preferably ~rom 5:1 to t 100 ~.
Efficient catalysts are ~ewis acids and the metal ortransition metal compounds generating the same. ~he Iewis acids may be employed as such or mixed with one another; use may also be made of adducts thereof with organic molecules. Preferred catalysts are compounds having the formulae AlX3, TiX3, UX4, TiX4, VoX3~ VX5, ZnX2, ~eX3 and SnX4, wherein X is halogen, acetoxy, alcoxy or aryloxy.
~ he process according to the in~ention may be utilized for preparing aromatic derivatives other than those mentioned above, for instance aromatio thlocarbonates or imido-carbonates starting ~rom the corresponding alkyl compounds. Moreover, it is possible, to prepare polymeric carbonates contsining in the molecule repeating units of the type ~A-O_C0_0~ in which A is a divalent radical con-taining at least one aromatic ~unction. These polymeric carbonates are obtained~ in accordance with a further aspect of the invention, ;~
by carrying out the aforesaid reaction while removing thQ alkyl oarbonate, ~ he subJeob invention will now ~e further understood with referonoe to the following non restrictive exam~les. In these example~ the reagent3 and the catalyst were charged in a 2 1 ~lask ~itted with a 10 plate distilling column having a liquid-dividing hsad5 th~ lo~ boiling aloohols were oontinuously distilled eithe~r ~ uch or in the form of azeotropes. ~he ~eactions w~re carried out under an inert atmosphere, the reagents and solvent employed ~30 having been suitably rendered anhydrous.
E~ MPIE 1 Reaction between dimethylcarbona~e (DMC) and phenol (phen) was carried out in presence of anhydrou~ AlCl~ in a DMC/Phen/cat :
.
, .
1~)39740 molar ratio of 5/1/0.05. The temperature was 98C; a methyl alcohol _DMC azeotro~e wa9 distilled at a reflux ratio of 10:1.
After 8 hours, a phenol conversion equal to 15.5% and a pheny-lmethylcarbonate (PhMC) selectivity of 95% were obtained, the re_ maining 5% of phenol having been converted to anisole.
EX~MPIE 2 ~ he reaction was carried out under the same conditions as in example 1~ but the catalyst utiliæed was TiC13. After 5.5 hours~ a phenol conversion of 13% and a Ph MC sele¢ti~ity higher than 99% were obtained.
. ~ .
The reaction was carried out as in example 1. ~iC14 wa~
u~ed as cataly~t. After 8 hours, conversion of 23% and a total ~ele¢tivity with rQspect to Ph MC were obtained.
EX~MPIE 4 ~ he same conditions as in example 1 were retained, except that ~i(0-isopropyl)4 was employed as catalyst. After 8 hours, a conversion ef 11% and a practically total selectivity ~ith respect to Ph MC were obtained.
'.
E MPIE ~
The same condition~ a~ in example 1 were retained, except that ~i(od)4 Wa9 employed as employed as cataly~t. After 24 hours~
a eonver~ion of 41.5% and a ~electivity with respeot to Ph MC of 95% were obtained~ the remaining part consisting of diphenylcarbonate (Dpha). Anisole was present only as traces, ~hich could not be evsluated from an analytical point of view. ~ ;
~ ~ .
Under the same conditions as in example 1, VC14 was utllized a8 oatalyst. A conversion of 3% and a total selectivity with respect to phenylmethylcarbonate ~ere obtained.
-3~
, : , . .' ' - ,:
EXAMPIE ~ 1039740 VOC13 was employed as cataly~t in the reaction conditions of example 1. After 5 hours, a phenol conversion o~ 5~ and a total selectivity with respect to phenylmethylcarbonate were - -obtained. ~
- .
E-X~MPIE 8 ~ -~ he same conditions as in example 6 ~ere retained, except that use was made of a DMC/Phen/Ti(00)4 molar ratio of 10/1/0.05.
After 8 hours, a phenol conversion of 21% and a practically total ~electivity with re~pect to Ph~lC were obtained.
, EX~MPIE g --The reaotion ~as carried out with mixture formed by DMC/
Phen/~iCl in a molar ratio of 1/4/0.05, in presence of n-hexane ~n an a-mount corresponding to 35 g per m~le of D~C. A mixture consisting of hexane/DMC/Methyl alcohol na9 distilled at a reflux ~-ratio of 10/1 and added a mixture of hexane/DMC was continuously added ~u¢h a~ to reinstate the portion ~emoved by distillation.
The reaction temperature was 135C. After 8 hours, a phenol con-- vereion of 9%~ a Phen MC selectivity of 78% and a D Phen C ~electi-vity o~ 22% were obtained.
;. . ~
EXA~MPI~ 1 ~ he reaotion was carried out at 130C with a mixture oonsisting of p-cresole/DEC (diethylcarbonate)/~i(0-iC3E7)4 in a molar ratio of 1/5/0.05~ over a period of 3 hours, A conver~ion o~ 25% and a total selectivity ~ith respeot to tolyl-ethyl-car-bonate were obtained.
- , , -A mixture of ~EC/hydroquinone-mo-nomathylether/~i(O_i C3H7)4 in a molar ratio of ratio 5/1/0.05 were reacted at 130C over a ~30 perlod of 3 hours. A oonvffrsion of 36~ and a practically total _4_ ~: f 1~39740 electivity with respect to p-methoxiphenylcarbonate were obtained Phenylethylcarbonate wa3 reacted with phenol in the presence of Ti(00)4, in a molar ratio of 1~0.8/0.04, at 180C, and in heptane. A mixture consisting of n-hept~ne-ethyl alcohol and n-heptane was continuou~ly distilled and wa~ added to the reaction medium for replacing the distilled fraction~ After 4 hours, a phenol conversion of 42% and a total selectivity with respect to diphenylcarbonate were obtained.
E~AMPIE 13 Use was made of a stainless steel reactor having a volume of 2,4 1, which was fitted with a steel ~istillation column having 1" in diameter and 1 m in length and packed with glass rascings.
~he reaction was carried out at 180C and at 6.6 Atm by continuous-ly distilling the methyl alcohol, _DMC azeotrope and renewing the DMC removed throuth distillation. ~he DMC/Phen/Ti(00)4 molar ratio Wa9 5/1/0.5. After a reaction period of 7 hours, a phenol conver-~ion of 53%, a sele¢tivity with respect to PhMC of 95% and a ~electivity ~ith respect to DPhC of 5% were obtained ~he ~ame conditions as in example 1 were retained, except that SnC14 was employed as catalyst, ~he conversion obtained was 8%~ the selectivity ~ith respect to phen~lmethylcarbonste wa~ 85%
and with respect to phenylmethylether 15%.
A mixture of rEC/Phen/UCl4 wa9 reacted, in a molar ratio of 5/1/0.075~ at 130C and over a period of 4 hour~. A phenol con-~r~ion of 38% was obtained with selecti~ities with respect to Phen EC of 98% and to ~EC of 2%.
:: :: :
1~)39740 A mixture of IEC/p-nitrophenol/Ti(00)4 in a molar ratio of ratio 5/1/0.05 wa9 reacted at 130C and over a period o~ 4 hours. A p-nitrophenol conversion of 10% and a total selectivit~
with respect to p-nitrophenyl-carbonate were obtained.
Use wa~ made of a 250 cc flask provided with a distilla-tion column having 20 plates and equipped with a liquid-dividing head; 68 g of phenyl acetate, 60 g of diethylcarbonate and 2 g o~
titanium phenate were charged therein, at 145C. ~y continuously head distilling ethyl acetate, 68% by mole of diphenyl carbonate nnd 30% by mole of phenyl-ethyl-carbonate at a total 3electivity higher than 98% and a conver~ion of phenyl acetate of 95% were obtained after a reaction period of 4 hour3.
.~ .
~ In the apparatu~ of example 17, at 145C, were charged ; 74 g of phenol acetate and, gradually, 90 g of dimethyl carbonate and 1 g of titanium tetramethoxide. Methyl acetate wa~ continuous-ly di3tilled and, after 4 hours~ BO~o by mole of diphenyl carbonate ;~20 and 18% by mole o~ ph~nol m~thyl oàrbonate n~re obtainQd, at a eeleotivity higher than 9~% and a oonYer~ion of methyl acetat~ o~
~` 97%-BX~MPIæ 19 . .
~; In thQ same apparatu~ described in example 17 were charged, at 150C, 68 g of phenyl a¢etate, 80 ~ of phenyl methyl carbonate and 25 cc of n-heptane with 1.5 g of aluminium ethylate. Methyl aoetate ~a3 continuou~Iy distilled and, after 4 hours, a conversion ~ ... ..
of ;90~0 and a ~electivity with respect to diphenyl carbonate. `
EXA~PIE 20 ;~ 150 g of bisphenol A bis acetate and 3 cc of titanium .
1~39740 tetrai~opropylate ~ere charged, at 140-150C, in the apparatus of example 17, then 130 cc of diethylcarbonate were gradually added while ethyl ~cetate was continuouslg distilled from the system.
After 10 hours, a total conversion of bisphenol acetate to bi- _ sphenol A - bis ethyl carbon~te wa~ obtained. -~
In the same apparatus described in example 17 were charged 150 g of bisphenol A bis~cetate ~nd 3 g of aluminium tetraiso-propylate, at 150-170C, and there were gradually added 110 cc of demethyl carbonate~ methyl acetate being continuously distilled.
After 8 hours, a complete conversion t bisphenol bis methyl car-bonate was obtained.
. '.
EXAMPIE 2~
190 g o~ bi~phenol A bis-aceta~e and 2.5 g of ~i(0-i~o C ~7)4 were charged into a 250 cc flask fitted with a distilling column having 30 plates and equipped with a liquid - dividing hesd. ~he mixture ~as heated at 150-170C~ and was then gr~duaily added with 160 cc of dimethylcarbonate. In the same time methyl aoetate wa~ formed, which distilled off when the reaction was completed~ the system was brought under ~aouum and the temperature rai3ed up to 270QC. Dimeth~lcarbonate~ which distilled during the reaction~ ~a~ recovered by means of a cold trap. After 4 hours, a polymer ha~ing an average molecular weight of 17~000 and a ~truoture corre~ponding to oommercial aromatic polycarbonates wa~
obtained.
.
.
E~ MPIES 23-24 wo tests were carried out according to the procedure of :, .. ::: ;!:
the precedin~ e~ample. ~he amounts Or the compounds employed and the re3ults obtained are reported in the following table.
, .
~ 30 ` ~ -. ~. .
~ 7_ ~
,. ~ . .
~;)3~740 -Alkyl carbonate Catalyst ~isphenol PolymRr molecular ~eigh~
diethylcarbonate ~i(O0)4 acetate 1S0 cm 2.5 g 150 g 14,000 ~ -dimethylcarbonate Al(0_~ec butyl)3 .
150 cm3 3 g 150 g 5~600 -.
~ :','' ~ . :
~ ' . ' ' : .' .:
. . . .
:.~ :..
: .
.
: . .
~ . .
` ~ , ' ' : ' ' 1 ~ 8 . ~
: ( ~ ' ' ...... . ~ ... .; . " . , ,.,.. . .. . . ... ,, . . ~ . ..... ~ .... ........... . . ... . .. .
O
~ O_C_OR' (1-5) wherein R i9 an alkyl, alkoxy, aryl or aryloxy radicsl or a nitro group and Rl is an alkyl group or a radical of the formula:
~ : '.
(1-5) ' ' in which R has the nforesaid meanings.
M~thod~ for the preparation of these compounds are known~
starting from the corresponding phenols through a reaotion with phosgene or chloroformiates according to complex technologies.
These however, present several risks due to the toxioity of the reagents employed and give rise to the formation of hydrochloric aoid 8~ by-product. ~ ;
On the other hand, it i~ also known to react phenols and alkyl carbonates in preeence of ~trong ba~es aa oataly~t, Such a reaotion ha~ however the drawbaok of lo~ reaotion rate~ and the ~ormation of high amounts of phenol ether as by-products.
Aromatio carbonates ha~e a remarkable industrial applica-t~on ~ince they can be employed as intermediates in the produ¢tion ~ . .
;~ Or aromatic polyoarbonates and in the synthesi~ of various isocy-.
anate~.
It has no~ been found that it is possible to obtain, at . ~
~ hi p yields and selectivities, aryl-alkyl carbonates and diaryl : : , carbonates according to the present in~ention, these are obtained by reacting the corresponding phenQls or acyl esters thereof with ;alkyl cyclic or aryl-alkyl carbonates, in the presence of suitable ~catalys~t~ he reaction i9 carried out in the liquid pha~e, ~ith ,;; ,.'.'. ;:,, ,~', ~"; ',"',''";."."'' ;
~)39740 - ~
or without a solvent, at a temperature of from 25 to 350C, pre-ferably from 80 to 250~, and 8 pressure of from 0.1 to 100 atm "
pre~erably from 1 to 25 atm.
The molar ratio between the phenol and carbonate com-pounds may range from 100:1 to 1:100, preferably ~rom 5:1 to t 100 ~.
Efficient catalysts are ~ewis acids and the metal ortransition metal compounds generating the same. ~he Iewis acids may be employed as such or mixed with one another; use may also be made of adducts thereof with organic molecules. Preferred catalysts are compounds having the formulae AlX3, TiX3, UX4, TiX4, VoX3~ VX5, ZnX2, ~eX3 and SnX4, wherein X is halogen, acetoxy, alcoxy or aryloxy.
~ he process according to the in~ention may be utilized for preparing aromatic derivatives other than those mentioned above, for instance aromatio thlocarbonates or imido-carbonates starting ~rom the corresponding alkyl compounds. Moreover, it is possible, to prepare polymeric carbonates contsining in the molecule repeating units of the type ~A-O_C0_0~ in which A is a divalent radical con-taining at least one aromatic ~unction. These polymeric carbonates are obtained~ in accordance with a further aspect of the invention, ;~
by carrying out the aforesaid reaction while removing thQ alkyl oarbonate, ~ he subJeob invention will now ~e further understood with referonoe to the following non restrictive exam~les. In these example~ the reagent3 and the catalyst were charged in a 2 1 ~lask ~itted with a 10 plate distilling column having a liquid-dividing hsad5 th~ lo~ boiling aloohols were oontinuously distilled eithe~r ~ uch or in the form of azeotropes. ~he ~eactions w~re carried out under an inert atmosphere, the reagents and solvent employed ~30 having been suitably rendered anhydrous.
E~ MPIE 1 Reaction between dimethylcarbona~e (DMC) and phenol (phen) was carried out in presence of anhydrou~ AlCl~ in a DMC/Phen/cat :
.
, .
1~)39740 molar ratio of 5/1/0.05. The temperature was 98C; a methyl alcohol _DMC azeotro~e wa9 distilled at a reflux ratio of 10:1.
After 8 hours, a phenol conversion equal to 15.5% and a pheny-lmethylcarbonate (PhMC) selectivity of 95% were obtained, the re_ maining 5% of phenol having been converted to anisole.
EX~MPIE 2 ~ he reaction was carried out under the same conditions as in example 1~ but the catalyst utiliæed was TiC13. After 5.5 hours~ a phenol conversion of 13% and a Ph MC sele¢ti~ity higher than 99% were obtained.
. ~ .
The reaction was carried out as in example 1. ~iC14 wa~
u~ed as cataly~t. After 8 hours, conversion of 23% and a total ~ele¢tivity with rQspect to Ph MC were obtained.
EX~MPIE 4 ~ he same conditions as in example 1 were retained, except that ~i(0-isopropyl)4 was employed as catalyst. After 8 hours, a conversion ef 11% and a practically total selectivity ~ith respect to Ph MC were obtained.
'.
E MPIE ~
The same condition~ a~ in example 1 were retained, except that ~i(od)4 Wa9 employed as employed as cataly~t. After 24 hours~
a eonver~ion of 41.5% and a ~electivity with respeot to Ph MC of 95% were obtained~ the remaining part consisting of diphenylcarbonate (Dpha). Anisole was present only as traces, ~hich could not be evsluated from an analytical point of view. ~ ;
~ ~ .
Under the same conditions as in example 1, VC14 was utllized a8 oatalyst. A conversion of 3% and a total selectivity with respect to phenylmethylcarbonate ~ere obtained.
-3~
, : , . .' ' - ,:
EXAMPIE ~ 1039740 VOC13 was employed as cataly~t in the reaction conditions of example 1. After 5 hours, a phenol conversion o~ 5~ and a total selectivity with respect to phenylmethylcarbonate were - -obtained. ~
- .
E-X~MPIE 8 ~ -~ he same conditions as in example 6 ~ere retained, except that use was made of a DMC/Phen/Ti(00)4 molar ratio of 10/1/0.05.
After 8 hours, a phenol conversion of 21% and a practically total ~electivity with re~pect to Ph~lC were obtained.
, EX~MPIE g --The reaotion ~as carried out with mixture formed by DMC/
Phen/~iCl in a molar ratio of 1/4/0.05, in presence of n-hexane ~n an a-mount corresponding to 35 g per m~le of D~C. A mixture consisting of hexane/DMC/Methyl alcohol na9 distilled at a reflux ~-ratio of 10/1 and added a mixture of hexane/DMC was continuously added ~u¢h a~ to reinstate the portion ~emoved by distillation.
The reaction temperature was 135C. After 8 hours, a phenol con-- vereion of 9%~ a Phen MC selectivity of 78% and a D Phen C ~electi-vity o~ 22% were obtained.
;. . ~
EXA~MPI~ 1 ~ he reaotion was carried out at 130C with a mixture oonsisting of p-cresole/DEC (diethylcarbonate)/~i(0-iC3E7)4 in a molar ratio of 1/5/0.05~ over a period of 3 hours, A conver~ion o~ 25% and a total selectivity ~ith respeot to tolyl-ethyl-car-bonate were obtained.
- , , -A mixture of ~EC/hydroquinone-mo-nomathylether/~i(O_i C3H7)4 in a molar ratio of ratio 5/1/0.05 were reacted at 130C over a ~30 perlod of 3 hours. A oonvffrsion of 36~ and a practically total _4_ ~: f 1~39740 electivity with respect to p-methoxiphenylcarbonate were obtained Phenylethylcarbonate wa3 reacted with phenol in the presence of Ti(00)4, in a molar ratio of 1~0.8/0.04, at 180C, and in heptane. A mixture consisting of n-hept~ne-ethyl alcohol and n-heptane was continuou~ly distilled and wa~ added to the reaction medium for replacing the distilled fraction~ After 4 hours, a phenol conversion of 42% and a total selectivity with respect to diphenylcarbonate were obtained.
E~AMPIE 13 Use was made of a stainless steel reactor having a volume of 2,4 1, which was fitted with a steel ~istillation column having 1" in diameter and 1 m in length and packed with glass rascings.
~he reaction was carried out at 180C and at 6.6 Atm by continuous-ly distilling the methyl alcohol, _DMC azeotrope and renewing the DMC removed throuth distillation. ~he DMC/Phen/Ti(00)4 molar ratio Wa9 5/1/0.5. After a reaction period of 7 hours, a phenol conver-~ion of 53%, a sele¢tivity with respect to PhMC of 95% and a ~electivity ~ith respect to DPhC of 5% were obtained ~he ~ame conditions as in example 1 were retained, except that SnC14 was employed as catalyst, ~he conversion obtained was 8%~ the selectivity ~ith respect to phen~lmethylcarbonste wa~ 85%
and with respect to phenylmethylether 15%.
A mixture of rEC/Phen/UCl4 wa9 reacted, in a molar ratio of 5/1/0.075~ at 130C and over a period of 4 hour~. A phenol con-~r~ion of 38% was obtained with selecti~ities with respect to Phen EC of 98% and to ~EC of 2%.
:: :: :
1~)39740 A mixture of IEC/p-nitrophenol/Ti(00)4 in a molar ratio of ratio 5/1/0.05 wa9 reacted at 130C and over a period o~ 4 hours. A p-nitrophenol conversion of 10% and a total selectivit~
with respect to p-nitrophenyl-carbonate were obtained.
Use wa~ made of a 250 cc flask provided with a distilla-tion column having 20 plates and equipped with a liquid-dividing head; 68 g of phenyl acetate, 60 g of diethylcarbonate and 2 g o~
titanium phenate were charged therein, at 145C. ~y continuously head distilling ethyl acetate, 68% by mole of diphenyl carbonate nnd 30% by mole of phenyl-ethyl-carbonate at a total 3electivity higher than 98% and a conver~ion of phenyl acetate of 95% were obtained after a reaction period of 4 hour3.
.~ .
~ In the apparatu~ of example 17, at 145C, were charged ; 74 g of phenol acetate and, gradually, 90 g of dimethyl carbonate and 1 g of titanium tetramethoxide. Methyl acetate wa~ continuous-ly di3tilled and, after 4 hours~ BO~o by mole of diphenyl carbonate ;~20 and 18% by mole o~ ph~nol m~thyl oàrbonate n~re obtainQd, at a eeleotivity higher than 9~% and a oonYer~ion of methyl acetat~ o~
~` 97%-BX~MPIæ 19 . .
~; In thQ same apparatu~ described in example 17 were charged, at 150C, 68 g of phenyl a¢etate, 80 ~ of phenyl methyl carbonate and 25 cc of n-heptane with 1.5 g of aluminium ethylate. Methyl aoetate ~a3 continuou~Iy distilled and, after 4 hours, a conversion ~ ... ..
of ;90~0 and a ~electivity with respect to diphenyl carbonate. `
EXA~PIE 20 ;~ 150 g of bisphenol A bis acetate and 3 cc of titanium .
1~39740 tetrai~opropylate ~ere charged, at 140-150C, in the apparatus of example 17, then 130 cc of diethylcarbonate were gradually added while ethyl ~cetate was continuouslg distilled from the system.
After 10 hours, a total conversion of bisphenol acetate to bi- _ sphenol A - bis ethyl carbon~te wa~ obtained. -~
In the same apparatus described in example 17 were charged 150 g of bisphenol A bis~cetate ~nd 3 g of aluminium tetraiso-propylate, at 150-170C, and there were gradually added 110 cc of demethyl carbonate~ methyl acetate being continuously distilled.
After 8 hours, a complete conversion t bisphenol bis methyl car-bonate was obtained.
. '.
EXAMPIE 2~
190 g o~ bi~phenol A bis-aceta~e and 2.5 g of ~i(0-i~o C ~7)4 were charged into a 250 cc flask fitted with a distilling column having 30 plates and equipped with a liquid - dividing hesd. ~he mixture ~as heated at 150-170C~ and was then gr~duaily added with 160 cc of dimethylcarbonate. In the same time methyl aoetate wa~ formed, which distilled off when the reaction was completed~ the system was brought under ~aouum and the temperature rai3ed up to 270QC. Dimeth~lcarbonate~ which distilled during the reaction~ ~a~ recovered by means of a cold trap. After 4 hours, a polymer ha~ing an average molecular weight of 17~000 and a ~truoture corre~ponding to oommercial aromatic polycarbonates wa~
obtained.
.
.
E~ MPIES 23-24 wo tests were carried out according to the procedure of :, .. ::: ;!:
the precedin~ e~ample. ~he amounts Or the compounds employed and the re3ults obtained are reported in the following table.
, .
~ 30 ` ~ -. ~. .
~ 7_ ~
,. ~ . .
~;)3~740 -Alkyl carbonate Catalyst ~isphenol PolymRr molecular ~eigh~
diethylcarbonate ~i(O0)4 acetate 1S0 cm 2.5 g 150 g 14,000 ~ -dimethylcarbonate Al(0_~ec butyl)3 .
150 cm3 3 g 150 g 5~600 -.
~ :','' ~ . :
~ ' . ' ' : .' .:
. . . .
:.~ :..
: .
.
: . .
~ . .
` ~ , ' ' : ' ' 1 ~ 8 . ~
: ( ~ ' ' ...... . ~ ... .; . " . , ,.,.. . .. . . ... ,, . . ~ . ..... ~ .... ........... . . ... . .. .
Claims (10)
1. A process for the preparation of aromatic carbonates having the general formula:
wherein R is an alkyl, alkoxy, aryl or aryloxy radical or a nitro group and R1 is an alkyl group or a radical of the formula:
in which R has the aforesaid meaning, which comprises reacting corresponding phenols or aryl esters thereof with alkyl, cyclic or aryl-alkyl carbonates, in the presence of a catalyst selected among Lewis acids, metal and transition metal compounds generating the same.
wherein R is an alkyl, alkoxy, aryl or aryloxy radical or a nitro group and R1 is an alkyl group or a radical of the formula:
in which R has the aforesaid meaning, which comprises reacting corresponding phenols or aryl esters thereof with alkyl, cyclic or aryl-alkyl carbonates, in the presence of a catalyst selected among Lewis acids, metal and transition metal compounds generating the same.
2. Process according to claim 1, wherein the catalyst is selected from the group comprising AlX3, UX4, TiX3, TiX4, VOX3, VX5, ZnX2, FeX3, SnX4 in which X is halogen, alcoxy, aryloxy or acetoxy.
3. Process according to claim 1, wherein the reaction is carried out at a temperature of from 25 to 350°C.
4. Process according to claim 3, wherein the temperature is comprised between 80 and 250°C.
5. Process according to claim 1, wherein the reaction is carried out at a pressure of from 0.1 to 100 Atm.
6. Process according to claim 5, wherein the pressure is comprised between 1 and 25 Atm.
7. Process according to claim 1, wherein the phenol compound and the alkyl carbonate are reacted in a phenol to carbonate molar ratio of from 100 : 1 to 1 : 100.
8. Process according to claim 7, wherein the phenol to carbonate molar ratio is comprised between 5:1 and 1:10.
9. Process according to claim 1, wherein the reaction is carried out in liquid phase.
10. Process according to claim 1, wherein a phenol compound is reacted with an alkyl carbonate, in the presence of said catalyst, while removing the alkyl carbonate to form a polymeric carbonate containing repeating units of the formula:
?A-O-CO-O?
in which A is a divalent radical containing at least one aromatic group.
?A-O-CO-O?
in which A is a divalent radical containing at least one aromatic group.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2439374A IT1025023B (en) | 1974-06-25 | 1974-06-25 | PROCESS FOR THE PREPARATION OF HEDERICOL COMPOUNDS WITH TWO HETEROATOMS SEPARATED FROM A CARBON ATOM |
| IT2019175A IT1046381B (en) | 1975-02-12 | 1975-02-12 | Aromatic carbonates prepn. - by reacting a phenol, or its acyl ester, with alkyl, cyclic or aralkyl carbonate |
| IT2247275A IT1049414B (en) | 1975-04-18 | 1975-04-18 | Aromatic carbonates prepn. - by reacting a phenol, or its acyl ester, with alkyl, cyclic or aralkyl carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039740A true CA1039740A (en) | 1978-10-03 |
Family
ID=27273038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,892A Expired CA1039740A (en) | 1974-06-25 | 1975-06-23 | Process for the preparation of aromatic carbonates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1039740A (en) |
-
1975
- 1975-06-23 CA CA229,892A patent/CA1039740A/en not_active Expired
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