CA2109229A1 - Preparation of n-acylimidazoles - Google Patents
Preparation of n-acylimidazolesInfo
- Publication number
- CA2109229A1 CA2109229A1 CA002109229A CA2109229A CA2109229A1 CA 2109229 A1 CA2109229 A1 CA 2109229A1 CA 002109229 A CA002109229 A CA 002109229A CA 2109229 A CA2109229 A CA 2109229A CA 2109229 A1 CA2109229 A1 CA 2109229A1
- Authority
- CA
- Canada
- Prior art keywords
- anhydride
- recited
- carboxylic
- groups
- carbonyldiimidazole
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
Abstract
A process for the production of N-acylimidazoles by the reaction of a carboxylic anhydride with carbonyldiimidazole is disclosed.
The products are useful as chemical intermediates.
The products are useful as chemical intermediates.
Description
W092/l960~ 2 i ~ 9 ~ 2 PCT/US92/03322 PREPAR~TION OF N-ACYLIMXDA20LES
r :lgL~U~ L:r :L1~
A process for the product~on of ~-acyl~midazoles by the re~ctlon of a carboxylic anhydride with a carbonyldiimidazole is disclosed. The p~oducts are use~l as c~emical intermedi~tes.
10 3~:L.~
H. A. Staab, Angew. Chem. I~tl. Ed., ~ol. 1, pp. 351-367 (1962) describes varàous syntheses ~nd useg for N-acylimidazoles (called therein "imidazolides").
At pp. 355-56 the reaction o~ carbonyldiimidazoles with carboxylic acids, to g~ve one mole of N-acylimidazole, o~e mole~o~ C02 and one mole of imidazole per mol~ of : starting mz~erial is described. No meation is made in ~his a2ticle of reacting carboxylic ~nhydsides with a carbonyi d7.imidazole to orm N acylimidazoles.
It is the object of the presen~ invention to : provide a simple method for thP preparation of N-acylimidazoles which gives only easily remoYable C02 as a byproduct, And fully utili~es all of the imidazole roups in the:;ca~ony}d~imidazole (all of the îmidazole 25~`~ ~ oups become~N acylim~dazole).. ~
Thts inve~Sion concerns a pr~eess for the :: productlon ~f N-acylimid zoles, co~p~i5ing, contac~in~ a earbGxylic anhydride with a casbonyldiim~dazole.
: 30 ~3.~L15_2C_r~ 3~1D~
~: This invention co~cerns the pxoduction of acylimid?zoles by the reaction of a carboxylic anhydride with a ~arbonyldiimidazole ~herein sometimes abbre~iated CDI). The carbonyldiimidazole has the : 35 formula ''~ ~ :
.~; , , wo 92rl9600 P(~/l~!~i9200?~ ~
~,lo92,6,?.9 """
N~ 11 / ~N
I N--C ~l ~
b~/ W
. . .
The imidazole rings o~ the carbonyldlmldazole (and the 5 r~sulting acylimidazole) mzy ~e substl~uted in the 2, 4 or 5 posit~on. It is preferred ~hat ln the carbonyl-d~imidazole both ~m~dazole ri~gs are un~u~s~l~uted, ~ha~
the compound l,l'-carbonyldimidazole.
By the term N-zcylimidazole is meant a compound of ~0 the type o Il /~N
R7~C--N
\~
:wherein n acyl group is bound to ~he 1 pos'tion o~ an lS imidazole ring. Th~ group ~1 is hydroc3r~yl, which may be subs~ituted:with various subs~ituenks. The va~ious substituents on t~e im~dazole ring or attached to the groyp Rl should be ~nert under proce~s conditions.
: ` Th~ group Rl is derived from the carboxylic 20: ~h~dri~e used~ln~he process. Carboxylic ~nhydr~des ; . are well known to~those:sk~lled in~the ~`rt and con~a~n the group -CtO)-O-C~O)-, where the ~ee bo~ds are to hydrocarbyl or-substituted hyd~o~byl groups J such as the group Rl. Car~oxylic anhydrides m~y be cy~lic or .
:~: 2~ acyclic. Thus ~e car~oxylic anhydx~de m~y h~Ye ~he formula RlC~O)-O-C(O~ ; wherein each Rl i5 independently hydrocar~yl, cr both hydrocarbyl groups ~1 may be joined to each other to form a cyclic anhydride. Examples of acyclic carboxyl anhydrides usefu~ in th~ instant process are acetic anhydride, perfl~orobutyric ~:
f `^~ wo 92/19600 PCI~/US92~0332~
anhydride, tr~luoro~cet~c ~nhydr~de, be2~zolc anhydride, h~acanolc anhydride, zlnd meth~crylic anhy~rlde. Thes~
acyc~ic ~nhydrides m~y ~lso be QO called m~x~d anhydrides, sueh as acetic: propzurlo~:: anhydr~de. In the S c:ase of m~xed ~2~hydrides, ~wo N~ cyllmld~:zoles w~ll be o~tsl~ed, each deriv~d ~rom one o~ ~che ~cyl groups in the mixed anhydr~ de . Sy~unetrical ~nhyd.rides (bo~h groups the same) are pre~erred. ~ typical reaction of CDI with an acycllc c~rboxylic snhydrlde ~s:
o ~R~CO)~O ~ Cr)l ~ 2 R1--C ~ co2 Cyclic anhydrides are at so useful in the instant process . Examples of such cyclic anhydri des ~ nc lude, 15 : bu~ are slot limited to, succinic anhydride, male~ c anhydride, ph halic.~ anhydride, and ~taconic anhydxide.
Wherl a cyclic anhydride reacts wit~ a CDI, a compound c~nta~ g two ~-acylimidazole gro~ps wl}l be produced assuming only one anhydride ~roup per cyclic anhydride 20 molecule) ,~ s~nce the anhydride groups are al~rl~ c:on~ected :~ by ~che cyc~l1c struc~ure. ~or exasnple, :reaction of phthalic- a~hydside~::with a CDl proceeds as ~ollows:
`~ Pr~ I~ N
"N
CDI + ~ [~ I F
:~ 25 Examples of suitable substituents ~chat may be present ei~cher in ~he carboxylic anhydride (for example, the gr~up R1 ) or in the 2, 9 or 5 positions of the :~
, :
W092/196~ PCT/~S9 JO~ ~ ~
210~29 ~
imldazole ring of the CDI ~and hence al o p~e~ent i~ ~he N-acyllmidazole p~oduct), lncl~de, bu~ ~re not llmited to ether, es~er, amide, fluoro, c~loro, bro~o, a~d ~odo, s~d fo~ su~stltut~on in ~e im~dazol~ ri~g, hydrocæsbyl.
Any comb~natlon of subst~tue~ts i~ ~ny ~-the~e positlons ~y be present~
The ~arboxylic anhydrid~ may be p~r~ of a much larger ~olecule, such as a polymer. For example, the carboxylic a~hyd~ide m~y be malelc ~hydrid~ or itaconic anhydride tha~ has been lusually ~ree r~dically~
copol~merlzed wi~h other monomers, so that the a~hydride group remains intact. The carbo~ylic ~nhydride may also eonta~n more than one anhydride groupf as ln pyromellitic anhydride, or a plural~ty of anhydride groups as i~ the copolymers mentioned ~bo~e. It is preferred if ~he~anhydride groups in the c~polymer are : ~ycl~c. . ~ .
Whlle Yirtually any ratio of the ingxedie~ts will yield the desised::N-acylimidazsles, lt ls preferred lf the ratio of total anbydride groups to the CDI is about : 1. This insures ~he most efficient u~e of ~he starting : : matexials, and ob~iates the need for remo~al of ~nreacted starting materials, i.e., yields relatlvely p~re N-acy~ida201e directly. Of course if ~t is 2~ desired ~o:react o~ly part of the ~nhydr~de groups (as ln;a polymer co~t inin~ ~nhydride), less CDS would be used;
~ ~hile temperat-are is not c:ritlcal ~ ~orlYenient ~: ~ : reaction rates are obtained at about 0C to about 200C, :; ~ 30 preferably ~out 20C to~about 100C. The use of sol~ents is optional, and any solve~t u~ed should be -~: apr~tic. SolYents are particularly useful when the :~ ~ ingredien~s are ~o~miscible or onç or both of the `~ ingredient~ are solid at the process temperature. A
r :lgL~U~ L:r :L1~
A process for the product~on of ~-acyl~midazoles by the re~ctlon of a carboxylic anhydride with a carbonyldiimidazole is disclosed. The p~oducts are use~l as c~emical intermedi~tes.
10 3~:L.~
H. A. Staab, Angew. Chem. I~tl. Ed., ~ol. 1, pp. 351-367 (1962) describes varàous syntheses ~nd useg for N-acylimidazoles (called therein "imidazolides").
At pp. 355-56 the reaction o~ carbonyldiimidazoles with carboxylic acids, to g~ve one mole of N-acylimidazole, o~e mole~o~ C02 and one mole of imidazole per mol~ of : starting mz~erial is described. No meation is made in ~his a2ticle of reacting carboxylic ~nhydsides with a carbonyi d7.imidazole to orm N acylimidazoles.
It is the object of the presen~ invention to : provide a simple method for thP preparation of N-acylimidazoles which gives only easily remoYable C02 as a byproduct, And fully utili~es all of the imidazole roups in the:;ca~ony}d~imidazole (all of the îmidazole 25~`~ ~ oups become~N acylim~dazole).. ~
Thts inve~Sion concerns a pr~eess for the :: productlon ~f N-acylimid zoles, co~p~i5ing, contac~in~ a earbGxylic anhydride with a casbonyldiim~dazole.
: 30 ~3.~L15_2C_r~ 3~1D~
~: This invention co~cerns the pxoduction of acylimid?zoles by the reaction of a carboxylic anhydride with a ~arbonyldiimidazole ~herein sometimes abbre~iated CDI). The carbonyldiimidazole has the : 35 formula ''~ ~ :
.~; , , wo 92rl9600 P(~/l~!~i9200?~ ~
~,lo92,6,?.9 """
N~ 11 / ~N
I N--C ~l ~
b~/ W
. . .
The imidazole rings o~ the carbonyldlmldazole (and the 5 r~sulting acylimidazole) mzy ~e substl~uted in the 2, 4 or 5 posit~on. It is preferred ~hat ln the carbonyl-d~imidazole both ~m~dazole ri~gs are un~u~s~l~uted, ~ha~
the compound l,l'-carbonyldimidazole.
By the term N-zcylimidazole is meant a compound of ~0 the type o Il /~N
R7~C--N
\~
:wherein n acyl group is bound to ~he 1 pos'tion o~ an lS imidazole ring. Th~ group ~1 is hydroc3r~yl, which may be subs~ituted:with various subs~ituenks. The va~ious substituents on t~e im~dazole ring or attached to the groyp Rl should be ~nert under proce~s conditions.
: ` Th~ group Rl is derived from the carboxylic 20: ~h~dri~e used~ln~he process. Carboxylic ~nhydr~des ; . are well known to~those:sk~lled in~the ~`rt and con~a~n the group -CtO)-O-C~O)-, where the ~ee bo~ds are to hydrocarbyl or-substituted hyd~o~byl groups J such as the group Rl. Car~oxylic anhydrides m~y be cy~lic or .
:~: 2~ acyclic. Thus ~e car~oxylic anhydx~de m~y h~Ye ~he formula RlC~O)-O-C(O~ ; wherein each Rl i5 independently hydrocar~yl, cr both hydrocarbyl groups ~1 may be joined to each other to form a cyclic anhydride. Examples of acyclic carboxyl anhydrides usefu~ in th~ instant process are acetic anhydride, perfl~orobutyric ~:
f `^~ wo 92/19600 PCI~/US92~0332~
anhydride, tr~luoro~cet~c ~nhydr~de, be2~zolc anhydride, h~acanolc anhydride, zlnd meth~crylic anhy~rlde. Thes~
acyc~ic ~nhydrides m~y ~lso be QO called m~x~d anhydrides, sueh as acetic: propzurlo~:: anhydr~de. In the S c:ase of m~xed ~2~hydrides, ~wo N~ cyllmld~:zoles w~ll be o~tsl~ed, each deriv~d ~rom one o~ ~che ~cyl groups in the mixed anhydr~ de . Sy~unetrical ~nhyd.rides (bo~h groups the same) are pre~erred. ~ typical reaction of CDI with an acycllc c~rboxylic snhydrlde ~s:
o ~R~CO)~O ~ Cr)l ~ 2 R1--C ~ co2 Cyclic anhydrides are at so useful in the instant process . Examples of such cyclic anhydri des ~ nc lude, 15 : bu~ are slot limited to, succinic anhydride, male~ c anhydride, ph halic.~ anhydride, and ~taconic anhydxide.
Wherl a cyclic anhydride reacts wit~ a CDI, a compound c~nta~ g two ~-acylimidazole gro~ps wl}l be produced assuming only one anhydride ~roup per cyclic anhydride 20 molecule) ,~ s~nce the anhydride groups are al~rl~ c:on~ected :~ by ~che cyc~l1c struc~ure. ~or exasnple, :reaction of phthalic- a~hydside~::with a CDl proceeds as ~ollows:
`~ Pr~ I~ N
"N
CDI + ~ [~ I F
:~ 25 Examples of suitable substituents ~chat may be present ei~cher in ~he carboxylic anhydride (for example, the gr~up R1 ) or in the 2, 9 or 5 positions of the :~
, :
W092/196~ PCT/~S9 JO~ ~ ~
210~29 ~
imldazole ring of the CDI ~and hence al o p~e~ent i~ ~he N-acyllmidazole p~oduct), lncl~de, bu~ ~re not llmited to ether, es~er, amide, fluoro, c~loro, bro~o, a~d ~odo, s~d fo~ su~stltut~on in ~e im~dazol~ ri~g, hydrocæsbyl.
Any comb~natlon of subst~tue~ts i~ ~ny ~-the~e positlons ~y be present~
The ~arboxylic anhydrid~ may be p~r~ of a much larger ~olecule, such as a polymer. For example, the carboxylic a~hyd~ide m~y be malelc ~hydrid~ or itaconic anhydride tha~ has been lusually ~ree r~dically~
copol~merlzed wi~h other monomers, so that the a~hydride group remains intact. The carbo~ylic ~nhydride may also eonta~n more than one anhydride groupf as ln pyromellitic anhydride, or a plural~ty of anhydride groups as i~ the copolymers mentioned ~bo~e. It is preferred if ~he~anhydride groups in the c~polymer are : ~ycl~c. . ~ .
Whlle Yirtually any ratio of the ingxedie~ts will yield the desised::N-acylimidazsles, lt ls preferred lf the ratio of total anbydride groups to the CDI is about : 1. This insures ~he most efficient u~e of ~he starting : : matexials, and ob~iates the need for remo~al of ~nreacted starting materials, i.e., yields relatlvely p~re N-acy~ida201e directly. Of course if ~t is 2~ desired ~o:react o~ly part of the ~nhydr~de groups (as ln;a polymer co~t inin~ ~nhydride), less CDS would be used;
~ ~hile temperat-are is not c:ritlcal ~ ~orlYenient ~: ~ : reaction rates are obtained at about 0C to about 200C, :; ~ 30 preferably ~out 20C to~about 100C. The use of sol~ents is optional, and any solve~t u~ed should be -~: apr~tic. SolYents are particularly useful when the :~ ~ ingredien~s are ~o~miscible or onç or both of the `~ ingredient~ are solid at the process temperature. A
3~ useful solvent is methylene chl~ride. Use~ul solvent ::: :
, ::
, , ., , ~ . . - , .
~ W092/~96~ 2 1 0 ~ 2 2 ~ PCT/US92/03322 types include halocarbons, esters, aro~t~cs, etc.
Pxotic ~ol~ents such as alcohols, wa~er, pximary and ~econdary ~i~es ~hould be a~olde~.
It ~s prefer ~l~ ~o a~old w~ter ~por, 80 the S process ~s con~enl@ntly c~rr~ed out un~er a blanket o~
~trogen, ar~on, or C02. ~gl~at~on to aC~e~e mlxing Qf khe ingredients is pre~erred.
The product N-~cyl~midazole m2y be u~ed dtre~tly as made in ~he process, ~i~ce the only byproduct i5 gaseous la C02. ~f a solvent is u~ed, it ~ay be ~emoYed by distillation. The produc~ ~-acyli~idazole may be purified by distillation or crystalliza~ion, as appropriate.
As described by ~. A. S~a~b ~supra, which is hereby included by reference~, N-acyl~midazoles are useful lntermedia~es for ~he prep~at~on es~ers, amides, : peptides, carboxylic anhydrides, and other types o~
:: o~ganic compounds. This reference also describes ~he preparation of CDIs.
I~ the fol~ OW9 ng ~xamples, ~he CDI u~ed is ~ carbo~yldiimidazole. All parts are parts by :~ weight.
25 ~ Into 13 parts methylene chlor~de con~ai~ing 1.86 : p~rts carbonyldiim~idazole, 1.14 par~ acetic anhydride : was slowly added. Af~er 1 hour, ~he mlxture became cloudy. The solvent was removed to o~tain 2.37 par~s rude acetylimidazole, from which 1.31 parts ~: - 30 recry-c~allized ~roduct was obtained ~rom toluene.
:~ ~A-NMR and melting point were consistent with au~hentir cetylimidazole.
: , .
, W09~/~9600PCT/U~92/03~ ~ ~
$2;a~,~
~b~
Into 39 parts ~ethylene chlorlde contal~ing 9.83 parts ar~onyldiim~dazo~e, 9.35 p~rts neth~cryl~
anhydride was 810wly ~dded. G~ evolut~on beg~n lmmedlatoly; a~ter 1 hour ~he slurried mlx~ure bec~me cle~r, ~nd after 3 hours the gas evolutlon was compl~te.
The solvent was removed ~o obtain 17 parts crude product. A lS part fraction was d~stilled at 0.25 torr to obta~n 6.9 parts of a ~terlal dlstlll~ng ~rom 44 to 60C. ~R, lH-NMR, 13C NM~ were consistent with authentic ~aterial prepared by o her rou~es ~J. Polym. Sci., Polym. Chem. Ed., Vol. 12, pp. 2453~2455 51974)).
=I.
== ~L~
nto 132 parts methyle~e chloride containing 8.16 parts car~onyldilmidazole, 11.31 parts benzoic anhydride n 66 parts methyl~ne chloride wa~ added. Thc result~ng :: mix~ure was refluxed 5 hours until gas e~olut~on ceased.
;~ ~ ~ 20 ~he yield ~fter removal of solvent at reduced pressure : ~ was 19.31 pa~ts crude material, demons~rated as : predomi~antly benzoylimidazole by IR, GC-MS, lH-NMR, and 3C-NMR accompanied by some dichloromethane. The compound ~s~:~nown, Chem. Ber., ~ol. 95, pp. 1275-1283 :25 ~19~ s~
~ : Into a solution of 5.04 parts S~A-100 styrene/
:~ maleic anhydride copolymer (Atochem, Inc.) in 50 parts dichloromethane, there was~added a slurry of 5.09 parts carbonyldiimidazole in 10.1 parts ~ethyle~e hloride.
The resulting mixture was refluxed for twa hours. The ~:~ solids dissolv~d, g s was generated, and the mixture tur~ed a ~ery deep red. The IR absorbances at 1780 and 35 1857 c~-l (S~A-1000) and 1754 cm~l (carbonyldilmidazole) ;,~
'~
~ .
WO92/19600 2In~2~3 P~/US92 weré cc~mple~ely replaced in the product by absor~ce peaks at 1758, 1780, and 1730 cm-l.
S In~:o a mixture o~ 10 paEts per~lu~r~bu~yrlc ~r.hydr~de in 40 p~rts o~ dlchloromeS~ne, ~chcre w~s ~dd~d a ~lurry o~ 4 . O par~s c~onyld~mldazole in 10 . 25 parts methylene chloside. The resulting mlxtu~e w~s refluxed for one ho~r. Gas gener2~tlon was noted during the addltion and re lux s~eps . The IR ~sos3: a~ces at 1798 and 1866 cm~l ~a~hydride) ar~d 17$4 cm-l ~car~onyl-diimidazo~e ) were replaoed in the product by a peak at 1754 cm~l. ~he yield after remo~ral of sol~renat ~y vacuum was 12 . 3 par~s .
Although pre~erred embodime~ts o~ 1:he ~ n~Jesltion have ~een described here~nabo-Je, it ~15 to ~e understood that there ls ~o intention ~o ll~nit ~he lntrentivn to the : ~ p~eeis~ co~structions herein disclo~ed, and lt is ~o ~e 20 ~urther understood ~hat ~che riçlh~ ~s reser~ed ~:o all changes coming within the s~ope of the in~rention as ~: ~ defined by the appended claims.
,:
.~,' ~ ' 3~
:
3 ~
~ .
~:
~ ~ .
::~
~ :
, ::
, , ., , ~ . . - , .
~ W092/~96~ 2 1 0 ~ 2 2 ~ PCT/US92/03322 types include halocarbons, esters, aro~t~cs, etc.
Pxotic ~ol~ents such as alcohols, wa~er, pximary and ~econdary ~i~es ~hould be a~olde~.
It ~s prefer ~l~ ~o a~old w~ter ~por, 80 the S process ~s con~enl@ntly c~rr~ed out un~er a blanket o~
~trogen, ar~on, or C02. ~gl~at~on to aC~e~e mlxing Qf khe ingredients is pre~erred.
The product N-~cyl~midazole m2y be u~ed dtre~tly as made in ~he process, ~i~ce the only byproduct i5 gaseous la C02. ~f a solvent is u~ed, it ~ay be ~emoYed by distillation. The produc~ ~-acyli~idazole may be purified by distillation or crystalliza~ion, as appropriate.
As described by ~. A. S~a~b ~supra, which is hereby included by reference~, N-acyl~midazoles are useful lntermedia~es for ~he prep~at~on es~ers, amides, : peptides, carboxylic anhydrides, and other types o~
:: o~ganic compounds. This reference also describes ~he preparation of CDIs.
I~ the fol~ OW9 ng ~xamples, ~he CDI u~ed is ~ carbo~yldiimidazole. All parts are parts by :~ weight.
25 ~ Into 13 parts methylene chlor~de con~ai~ing 1.86 : p~rts carbonyldiim~idazole, 1.14 par~ acetic anhydride : was slowly added. Af~er 1 hour, ~he mlxture became cloudy. The solvent was removed to o~tain 2.37 par~s rude acetylimidazole, from which 1.31 parts ~: - 30 recry-c~allized ~roduct was obtained ~rom toluene.
:~ ~A-NMR and melting point were consistent with au~hentir cetylimidazole.
: , .
, W09~/~9600PCT/U~92/03~ ~ ~
$2;a~,~
~b~
Into 39 parts ~ethylene chlorlde contal~ing 9.83 parts ar~onyldiim~dazo~e, 9.35 p~rts neth~cryl~
anhydride was 810wly ~dded. G~ evolut~on beg~n lmmedlatoly; a~ter 1 hour ~he slurried mlx~ure bec~me cle~r, ~nd after 3 hours the gas evolutlon was compl~te.
The solvent was removed ~o obtain 17 parts crude product. A lS part fraction was d~stilled at 0.25 torr to obta~n 6.9 parts of a ~terlal dlstlll~ng ~rom 44 to 60C. ~R, lH-NMR, 13C NM~ were consistent with authentic ~aterial prepared by o her rou~es ~J. Polym. Sci., Polym. Chem. Ed., Vol. 12, pp. 2453~2455 51974)).
=I.
== ~L~
nto 132 parts methyle~e chloride containing 8.16 parts car~onyldilmidazole, 11.31 parts benzoic anhydride n 66 parts methyl~ne chloride wa~ added. Thc result~ng :: mix~ure was refluxed 5 hours until gas e~olut~on ceased.
;~ ~ ~ 20 ~he yield ~fter removal of solvent at reduced pressure : ~ was 19.31 pa~ts crude material, demons~rated as : predomi~antly benzoylimidazole by IR, GC-MS, lH-NMR, and 3C-NMR accompanied by some dichloromethane. The compound ~s~:~nown, Chem. Ber., ~ol. 95, pp. 1275-1283 :25 ~19~ s~
~ : Into a solution of 5.04 parts S~A-100 styrene/
:~ maleic anhydride copolymer (Atochem, Inc.) in 50 parts dichloromethane, there was~added a slurry of 5.09 parts carbonyldiimidazole in 10.1 parts ~ethyle~e hloride.
The resulting mixture was refluxed for twa hours. The ~:~ solids dissolv~d, g s was generated, and the mixture tur~ed a ~ery deep red. The IR absorbances at 1780 and 35 1857 c~-l (S~A-1000) and 1754 cm~l (carbonyldilmidazole) ;,~
'~
~ .
WO92/19600 2In~2~3 P~/US92 weré cc~mple~ely replaced in the product by absor~ce peaks at 1758, 1780, and 1730 cm-l.
S In~:o a mixture o~ 10 paEts per~lu~r~bu~yrlc ~r.hydr~de in 40 p~rts o~ dlchloromeS~ne, ~chcre w~s ~dd~d a ~lurry o~ 4 . O par~s c~onyld~mldazole in 10 . 25 parts methylene chloside. The resulting mlxtu~e w~s refluxed for one ho~r. Gas gener2~tlon was noted during the addltion and re lux s~eps . The IR ~sos3: a~ces at 1798 and 1866 cm~l ~a~hydride) ar~d 17$4 cm-l ~car~onyl-diimidazo~e ) were replaoed in the product by a peak at 1754 cm~l. ~he yield after remo~ral of sol~renat ~y vacuum was 12 . 3 par~s .
Although pre~erred embodime~ts o~ 1:he ~ n~Jesltion have ~een described here~nabo-Je, it ~15 to ~e understood that there ls ~o intention ~o ll~nit ~he lntrentivn to the : ~ p~eeis~ co~structions herein disclo~ed, and lt is ~o ~e 20 ~urther understood ~hat ~che riçlh~ ~s reser~ed ~:o all changes coming within the s~ope of the in~rention as ~: ~ defined by the appended claims.
,:
.~,' ~ ' 3~
:
3 ~
~ .
~:
~ ~ .
::~
~ :
Claims (19)
1. A process for the production of N-acyl-imidazoles, comprising, contacting a carboxylic anhydride with a carbonyldiimidazole.
2. The process as recited in Claim 1 carried out in the presence of an aprotic solvent.
3. The process as recited in Claim 1 carried out at a temperature of about 0°C to about 200°C.
4. The process as recited in Claim 3 carried out at a temperature of about 20°C to about 100°C.
5. The process as recited in Claim 2 carried out at a temperature of about 0°C to about 200°C.
6. The process as recited in Claim 1 wherein the ratio of carboxylic anhydride groups to carbonyl-diimidazole is about 1.
7. The process as recited in Claim 3 wherein the ratio of carboxylic anhydride groups to carbonyl-diimidazole is about 1.
8. The process as recited in Claim 1 wherein said carboxylic anhydride has the formula R1C(O)-O-C(O)R1, wherein each R1 is independently hydrocarbyl, or both hydrocarbyl groups R1 are joined to each other to form a cyclic anhydride.
9. The process as recited in Claim 7 wherein said carboxylic anhydride has the formula R1C(O)-O-C(O)R1, wherein each R1 is independently hydrocarbyl, or both hydrocarbyl groups R1 are joined to each other to form a cyclic anhydride.
10. The process as recited in Claim 8 wherein each R1 is the same.
11. The process as recited in Claim 9 wherein each R1 is the same.
12. The process as recited in Claim 8 wherein said R1 contains one or more substituents selected from the group consisting of ether, ester, amide, fluoro, chloro, bromo, and iodo.
13. The process as recited in Claim 9 wherein said R1 contains one or more substituents selected from the group consisting of ether, ester, amide, fluoro, chloro, bromo, and iodo.
14. The process as recited in Claim 1 wherein said carboxylic anhydride is elected from the group consisting of acetic anhydride, perfluorobutyric anhydride, trifluoroacetic anhydride, benzoic anhydride, hexanoic anhydride, methacrylic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and itaconic anhydride.
15. The process as recited in Claim 7 wherein said carboxylic anhydride is elected from the group consisting of acetic anhydride, perfluorobutyric anhydride, trifluoroacetic anhydride, benzoic anhydride, hexanoic anhydride, methacrylic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and itaconic anhydride.
16. The process as recited in Claim 1 wherein said carbonyldiimidazole is 1,1'-carbonyldimidazole.
17. The process as recited in Claim 2 wherein said aprotic solvent is methylene chloride.
18. The process as recited in Claim 1 wherein said anhydride is a copolymer containing a plurality of cyclic anhydride groups.
19. The process as described in Claim 9 wherein said carbonyldiimidazole is 1,1'-carbonyldiimidazole.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/284,896 US5084280A (en) | 1988-12-15 | 1988-12-15 | Wood preservation composition and method |
| US07/695,157 | 1991-05-03 | ||
| US07/695,157 US5145983A (en) | 1988-12-15 | 1991-05-03 | Preparation of N-acylimidazoles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2109229A1 true CA2109229A1 (en) | 1992-11-04 |
Family
ID=40290953
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004637A Expired - Lifetime CA2004637C (en) | 1988-12-15 | 1989-12-05 | Water dispersible, ammonia-free wood preservative composition and method of preserved wood |
| CA002109229A Abandoned CA2109229A1 (en) | 1988-12-15 | 1992-04-29 | Preparation of n-acylimidazoles |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004637A Expired - Lifetime CA2004637C (en) | 1988-12-15 | 1989-12-05 | Water dispersible, ammonia-free wood preservative composition and method of preserved wood |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US5084280A (en) |
| EP (2) | EP0539619A1 (en) |
| JP (1) | JPH06507411A (en) |
| CA (2) | CA2004637C (en) |
| DE (2) | DE4126986A1 (en) |
| WO (1) | WO1992019600A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5084280A (en) * | 1988-12-15 | 1992-01-28 | Chapman Chemical Company | Wood preservation composition and method |
| US5470986A (en) * | 1994-06-27 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Imidazolium hardeners for hydrophilic colloid |
| US5846305A (en) * | 1996-01-16 | 1998-12-08 | Michael Wall & Sons Enterprises Ltd. | Liquid wood preservative solution |
| DE19614799A1 (en) * | 1996-04-15 | 1997-10-16 | Ostermann & Scheiwe Gmbh & Co | Process for the protection of laminated glulam and glulam from rot |
| DE19724884A1 (en) * | 1997-06-12 | 1998-12-17 | Basf Ag | Carbonyldiimidazoles, esters derived therefrom and processes for their preparation |
| SI1255752T1 (en) * | 2000-02-15 | 2007-12-31 | Pharmacia & Upjohn Co Llc | Pyrrole substituted 2-indolinone protein kinase inhibitors |
| AR042586A1 (en) | 2001-02-15 | 2005-06-29 | Sugen Inc | 3- (4-AMIDOPIRROL-2-ILMETILIDEN) -2-INDOLINONE AS INHIBITORS OF PROTEIN KINASE; YOUR PHARMACEUTICAL COMPOSITIONS; A METHOD FOR THE MODULATION OF THE CATALYTIC ACTIVITY OF PROTEINQUINASE; A METHOD TO TREAT OR PREVENT AN AFFECTION RELATED TO PROTEINQUINASE |
| CA2357357C (en) | 2001-09-17 | 2010-03-16 | Genics Inc. | Method of treating building materials with boron and building materials |
| EP1434774A1 (en) | 2001-10-10 | 2004-07-07 | Sugen, Inc. | 3-(4-substituted heterocyclyl)-pyrrol-2-ylmethylidene)-2-indolinone derivatives as protein kinase inhibitors |
| GB0700857D0 (en) * | 2007-01-17 | 2007-02-21 | Betts John A | Preservative compositions for wood and like materials |
| US8221797B2 (en) * | 2007-02-09 | 2012-07-17 | Osmose, Inc. | Wood preserving composition for treatment of in-service poles, posts, piling, cross-ties and other wooded structures |
| CN102633725A (en) * | 2012-04-10 | 2012-08-15 | 浏阳坛青达康医药科技有限公司 | Synthetic method of N-heptafluorobutyrylimidazole |
| US9303169B2 (en) | 2014-06-16 | 2016-04-05 | Osmose Utilities Services, Inc. | Controlled release, wood preserving composition with low-volatile organic content for treatment in-service utility poles, posts, pilings, cross-ties and other wooden structures |
| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2703023A1 (en) * | 1977-01-26 | 1978-07-27 | Basf Ag | FURANDERIVATE |
| CA1174004A (en) * | 1982-09-28 | 1984-09-11 | John Krzyzewski | Arsenical creosote wood preservative |
| US5084280A (en) * | 1988-12-15 | 1992-01-28 | Chapman Chemical Company | Wood preservation composition and method |
-
1988
- 1988-12-15 US US07/284,896 patent/US5084280A/en not_active Expired - Lifetime
-
1989
- 1989-12-05 CA CA002004637A patent/CA2004637C/en not_active Expired - Lifetime
-
1991
- 1991-05-03 US US07/695,157 patent/US5145983A/en not_active Expired - Lifetime
- 1991-08-15 DE DE4126986A patent/DE4126986A1/en not_active Withdrawn
- 1991-10-31 EP EP91118593A patent/EP0539619A1/en not_active Withdrawn
-
1992
- 1992-04-29 JP JP4511895A patent/JPH06507411A/en active Pending
- 1992-04-29 DE DE69213447T patent/DE69213447T2/en not_active Expired - Fee Related
- 1992-04-29 CA CA002109229A patent/CA2109229A1/en not_active Abandoned
- 1992-04-29 EP EP92911954A patent/EP0583375B1/en not_active Expired - Lifetime
- 1992-04-29 WO PCT/US1992/003322 patent/WO1992019600A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CA2004637A1 (en) | 1990-06-15 |
| JPH06507411A (en) | 1994-08-25 |
| DE4126986A1 (en) | 1993-02-18 |
| DE69213447D1 (en) | 1996-10-10 |
| EP0539619A1 (en) | 1993-05-05 |
| US5084280A (en) | 1992-01-28 |
| DE69213447T2 (en) | 1997-02-20 |
| US5145983A (en) | 1992-09-08 |
| EP0583375B1 (en) | 1996-09-04 |
| EP0583375A1 (en) | 1994-02-23 |
| CA2004637C (en) | 1996-12-24 |
| WO1992019600A1 (en) | 1992-11-12 |
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