CA1078396A - Process for preparing lower lactams from allylic substrates - Google Patents

Abstract

PROCESS FOR PREPARING LOWER LACTAMS FROM
ALLYLIC SUBSTRATES
(D#74,889-FB) ABSTRACT

This invention concerns processes for preparing cyclic, 5-membered ring, lactams through the carbonylation of allylic substrates in the presence of rhodium catalysts.

Description

`- 1078396 This invention relates to the catalytic conversion of allylic substrates to cyclic lactam products.
More particularly, this invention concerns processes for the synthesis of cyclic, 5-membered ring, lactams and their homologues through ;~
the carbonylation of allylic substrates, containing three or more carbon atoms, with carbon monoxide, in the presence of a catalytic amount of a homogeneous or heterogeneous rhodium catalyst, at elevated reaction con~
ditions of temperature and pressure. Two classes of allylic substrate may be employed in the inventive process, namely allylic amine substrates and allylic halides. Where the allylic substrate is an allylic halide, lactam synthesis is carried out in the presence of an amine co-reactant selected from the group consisting of ammonia or a primary amine of 1 to 12 carbon atoms.
The present invention provides the process of preparing ~ -butyro- -lactam or an alkyl-substituted- ~-butyrolactam by the carbonylation of allylic halides having three to 10 carbon atoms, said halides selected from the group consisting of chlorides, bromides and iodides by the procedure of:
(a) admixing said allylic halides to be carbonylated to ~-butyrolactam or an alkyl-substituted- ~-butyrolactam with at least a stoichiometric amount of amine coreactant selected from the group consisting of ammonia and primary amines having 1 to 12 carbon, with at least a catalytic amount of rhodium catalyst selected from the group consisting of:
Chlorobis ~ethylene) rhodium(I) dimer Chlorotris (triphenylphosphine) rhodium(I) Chlorocarbonylbis (triphenylphosphine~ rhodium(I) Rhodium tris (acetylacetonate) Rhodium chloride plus triphenylphosphine and Rhodium chloride to form a reaction mixture;
(b) pressurizing said reaction mixture with at least sufficient carbon B ''' - :
". " , .~ , ., " . , . " . .,.. "

: monoxide to satisfy the stoichiometry of the carbonylation to the ~ -butyrolactam or an alkyl-substituted- ~-butyrolactam; (c) heating said pressurized reaction mixture between about 20C. and 250C. and higher, :
until said allylic halide is carbonylated and ~-butyrolactam or an alkyl- ; ;
substituted- ~-butyrolactam is prepared, and isolating said lactams contained `. therein.
` The present invention also provides the process of preparing an alkyl-substituted- ~-butyrolactam by the carbonylation of allylic halides :;
having 3 to 10 carbon atoms, selected from the group consisting of chlor~des~ :~
bromides and iodides by the procedure of: (a) admixing said allylic halides to be carbonylated to an alkyl-substituted- ~-butyrolactam with at least a stoichiometric amount of an amine reactant selected from the group con-sisting of primary amines and secondary amines, said amines having 1 to 12 carbon atoms, with at least a catalytic amount of rhodium catalyst selected : from the group consisting of:
Chlorobis (ethylene) rhodium(I) dimer - .
Chlorotris (Triphenylphosphine) rhodium(I) Chlorocarbonylbis (triphenylphosphine) rhodium~
Rhodium tris ~acetylacetonate) and Rhodium chloride plus triphenylphosphine, said rhodium catalysts being bonded to an inert organic polymer, said inert ~`
organic polymer being selected from the group consisting of styrene, divinylbenzene polymers with appended nitrogen and phosphorus donor groups, to form a reaction mixture; (b) pressurizing said reaction mixture with at least sufficient carbon monoxide to satisfy the stoichiometry of the carbonylation to an alkyl-substituted- ~-butyrolactam; ~c) heating said pressurized reaction mixture between about 20C. and 250C. and higher, until said allylic halide is carbonylated and an alkyl-substituted- ~-butyrolactam is prepared, and isolating said alkyl-substituted- ~-butyro-lactam contained therein.

13 ~ la -~ ` 107~3396 The present invention also provides the process of preparing ~-butyrolactam by the carbonylation of allylic chloride having three to ten carbon atoms by the procedure of: (a) admixing said allylic chloride to be converted to ~ -butyrolactam with at least a stoichiometric amount of methylamine in the presence of iodide, with at least a catalytic amount of rhodium catalyst selected from the group consisting of:
Chlorobis (ethylene) rhodium(I) dimer ~ Chlorotris (triphenylphosphine) rhodium(I) -; Chlorocarbonylbis (triphenylphosphine) rhodium(I) . 10 Rhodium tris (acetylacetonate) -` Rhodium chloride plus triphenylphosphine, and Rhodium chloride, ; said rhodium catalysts bonded to an inert organic polymer being selected from the group consisting of styrene, divinylbenzene polymers with appended nitrogen and phosphorus donor groups, to form a reaction mixture; (b) pressur-izing said reaction mixture with at least sufficient carbon monoxide to satisfy the stoichiometry of the carbonylation to the ~ -butyrolactam;
(c) heating said pressurized reaction mixture between about 20DC. and 250~C.
and higher, until said allylic chloride is carbonylated and Y _butyrolactam is prepared, and isolating said ~-butyrolactam contained therein.
It is well documented in the literature that unsaturated compounds containing a nucleophilic group and a reactive hydrogen atom in a position which favors ring closure may react with carbon monoxide to give cyclic (ring) derivatives. This invention concerns the synthesis of 5-membered ring lactams and their homologues through the metal catalyzed carbonylation of allylic substrates. The invention process, as described therein, may be illustrated by the carbonylation reaction of equation (1) set forth below:
H

~ c=c c x + co + NH2 ~ ~ F + HX
~1) !
J
'' I ~ N/

iJ~-~ - lb -,~- ,.) ` ~ 107839~

wherein the desired product i9 a 5-membered ring lactam, the carbon valencies indicated are satisfied by hydrogen or alkyl, cycloalkyl, aryl, alkaryl or aralkyl groupings, each containing up to 12 carbon atoms, and X may be a halogen, chloride, bromide or iodi~e.
Alternatively, lactam synthesis may be effected from allylic amine substrates, as set forth in equation

(2), wherein again the carbon valencies indicated are satisfied by hydrogen or zlkyl, cycloalkyl, aryl, alkaryl or aralkyl groupings, each containing up to 12 carbon atoms.
, H ~ /
C--C
~C=C-C-NH + C~ (2) ~N ~ ~O
I
The practice of this invention, as set forth i~ equa-tion (1) and (2) is illustrated by:
1) The preparation of ~-butyrolactam from allylamine 2) The synthesis of ~~~utyrolactam from allylic halides in the presence of carbon monoxide and ammonia.

3~ The synthesis of alkyl-substituted- ~ butyrolactams from allylic halides in the presence of carbon monoxide an~ primary alkylamines.
The lactam products of this reaction are useful gen-erally as organic intermediates. ~-Butyrolactam, and its ho~ologues, for example, may be important in the manufacture of polyamides, and as solvents for the separation of aromatic, aliphatic mixtures.
The preparation of lactams from allylic precursors using metal carbonyl or carbonyl precursors as catalysts . .

.~, ` , . I

in the literature*. Reviews by Falbe** and others summarize this work, particularly the synthesis of 5-membered ring ~` lactams catalyzed by soluble cobalt catalysts. Unfortunate-ly, many of these metal catalysts of the prior art have the intrinsic disadvantages of requiring stringe~t reaction conditions, particularly allylic isomerization and polymer-ization reactions. Furthermore they exhibit poor selec-tivity to the desired product and require the use of allylic amines as the allylic precursor (equation 2~
This in~ention is directed to the use of certain homogeneous and heterogeneous rhodium catalysts which exhibit improved performances in the synthesis of 5-membered ring lactams, and their homologues, from allylic precursors. In practice this class of rhodium catalyst -allows lactam synthesis under significantly milder con-ditions of temperature and pressure than has hitherto been possible with other metal carbonyl catalysts of the prior art, e.~.,cobalt carbonyl catalysts. Furthermore, the rhodium catalysts of-this inv ention allow the formation of lactams in higher yields, with improved selectivities to desired product and higher catalyst turnover numbers than has been practical in the prior art. A further demonstrated advantage of these rhodium catalysts is that used catalyst samples remain active after carbonylation of an allylic substrate is complete. Consequently~ the used catalyst may be recycled with additional quantitities of allylic substrate while demonstrating similar specific carbonylation acti~ity to fresh catalyst material.

.
*J. Falbe and F. Korte, Chem. Ber. 98, 1928 (1965~.
- **"Carbon Monoxide in Organic Synthesis" by J. Falbe, Chapter IV, (1970).

In the broadest practice of this inventionj cyclic lactam products are produced from allylic precursors by the addition of carbon monoxide to an allylic material in the presence of a catalytic amount of rhodium catalyst, under elevated temperatures and pressures, in an oxygen-free environment, until the formation of the desired lactam products has taken place.
In the narrower practice of this invention, five-membered ring lactams and their homologues, containing at least 4 carbon atoms, are produced by the catalytic reaction `~
of carbon monoxide with an allylic halide by a process com-prising the fo}lowing steps: , a) Admixing each mole of allylic halide to be carbonylated with at least a stoichiometric amo~nt of an amine coreactant selected from the group consisting of ammonia or a primary amine, and at least a catalytic amount of homogeneous or heterogeneous rhodium catalyst, in the presence of a pressurized carbon monoxide atmosphere, to form a reaction mixture, and b) Heating said pressurized reaction mixture to 20C and above until substantial carbonylation of the allylic halide to the desired cyclic lactam derivative has taken place-and isolating said desired ~-lactam contained therein.
A further embodiment of the above described invention is the preparation of five-membered ring lactams and their homologues containing at least 4 carbon atoms by a process comprising the following steps:
.

.
. : : . .; ,, .. :

a) Admixing each mole of allylic amine to be carbonylated with at least a catalytic quantity of a homogeneous or heterogeneous rhodium catalyst in the presence of a pressurized atmosphere of carbon monoxide, to form a reaction mixture, and b) Heating said pressurized reaction mixture to 20C and above until substantial carbonylation of the allylic halide to the desired cyclic lactam derivative has taken `
place and isolating said desired ~-lactam contained therein.
In order to further aid in the understanding of -this invention, the following additional disclosure is ~-submitted:

PROCESS SEQUENOE AND VARIATIONS. In general, the components of the carbonylation reaction mixture, including optional inert solvent, allylic substrate, amine coreactant and rhodium catalyst may be added in any sequence as long as good agitation is employed throughout. The following respresent some variation insofar as the mode of catalyst addition is concerned, without departing from the inventive 0 concept. These modifications include:
a) The catalyst may be preformed and added pre-formed to the mixture of the other components to form the reaction mixture.
b) A substantial process variation that can be employed is when the catalyst is formed in situ in one or more components of the reaction mixture.

RHODIUM CATALYST. The use of a rhodium catalyst system is essential to the inventive carbonylation process. Either _5_ `~ 1078396 heterogeneous or homogeneous reaction mixtures may be employed in the practice of this invention. In the pre-ferred embodiment, rhodium complex catalysts which are soluble in the reaction mixture give good results. However, lactam synthesis may also be effected with catalysts which are not homogeneously distributed throughout the reaction mixture. Solid catalysts which remain in place during the course of reaction may be employed and suspensions of liquid and solid catalysts in the liquid media may also be employed. In suitable embodiments of this invention the rhodium complex compound can be used in combination with inert material or contained or deposited on porous supports such as alumina, silica-alumina, activated charcoal, titania, zirconia, zeolites as well as zeolitic molecular sieves. A pre~erred class of inert support for the rhodium catalysts of this invention are inert porous organic polymers.
The active form of the rhodium complex catalyst may be preformed prior to carbonylation, or it may be gen-erated 1n situ. Illustrative of rhodium containing substrates which can be conveniently used for effecting the carbonyl-ation of allylic substrates to lactams. include rhodium salts such as rhodium acetylacetonate, rhodium acetate dimer, rhodium formate, rhodium chloride, and rhodium dicarbonyl acetylacetonate, rhodium carbonyls such as hexarhodium hexadecacarbonyl tetrarhodium dodecacarbonyl dirhodium octacarbonyl, and chlorodicarbonyl rhodium(l), rhodium complexes with Group VB donor ligands such as chlorotris (triphenylphosphine~rhodium(I), chlorocarbonylbis(tri-phenylphosphine)rhodium(I), trichlorotris(pyridine) rhodium(III), hydridocarbonyltris(triphenylphosphine) - iO~8396 rhodium~I), chloropentaamminerhodium(III) chloride and dichlorotetramminerhodium(III) chloride, and rhodium olefin complexes such as bis(ethylene)rhodium(I) dimer, -chloro(1,5-cyclooctadiene)rhodium(I) dimer and chloro-norbornadiene rhodium(I) dimer.
Another preferred class of rhodium catalysts consists of the above classes of rhodium salts and com-plexes bonded to inert porous supports. A particularly favored embodiment of this invention is the use of these same rhodium salts and complexes bonded to inert porous organic polymers such as polystyrene polymers, cross-linked divinylbenzene-styrene copolymers, polyethylene and polypropylene-type polymers. These polymeric species may or may not also have appended nitrogen and phosphorus functional groups.
A further useful class of rhodium catalysts for the lactam synthesis are used catalyst sampies from prior preparations.
The quantity of catalyst employed is not narrow-ly critical and can vary over a wide range. In generalthe novel process is desirably conducted in the presence of a catalytically effective quantity of the active rhodium species which gives a suitable and reasonable reaction rate. Reaction proceeds when the rhodium concentration is as little as 0.01 mM, and even less. The upper limit is dictated and controlled primarily by economic factors in view of the exceedingly high costs of rhodium metal and its compounds. No particular advantages have been observed in using relatively high concentrations of rhodium catalyst.

ALLYL SUBSTRATES. As used throughout this disclosure, ~-this term refers to two related classes of allylic sub-strate, namely allylic halides and allylic amines, wherein the unsaturation (double bond~ in the substrate molecule is only between carbon-to-carbon atoms, and the halide or amine group is attached to the carbon atom one removed from the carbon atom of the double bond.
Suitable allylamine substrates have the general structure (A):

~ C=C-C-N~2 ~A) wherein the carbon valencies indicated are satisfied by hydrogen, or alkyl, cycloalkyl, aryl, alkaryl, or aralkyl groupings each containing up to 12 carbon atoms.
Illustrative of allylamines which are suitable precursors for lactam synthesis açcording to equation (2) include allylamine, 2-methylallylamine, 1-amino-2-decene, l-amino-3-ethyl-2-hexene, crotyl amine, 2-amino-3-pentene ' and 2 amino-2-methyl-3-butene.
When an allylic halide is the primary reaction substrate then ammonia or a primary amine must also be present in the carbonylation reaction mix in order for lactam formation to be achieved as depicted in equation (1). Suitable allyl halide substrates have the general structure (B):

~C=C-C-X (B) ~ -wherein the carbon valencies indicated are satisfied by hydrogen, or alkyl, cycloalkyl, aryl, alkaryl, or aralkyl groupings each containing up to 12 carbon atoms.

Illustrative of suitable allyl halide precursors for lactam synthesis according to equation (11 include allyl chloride, allyl bromide, allyl iodide, 2-methylallyl chloride, l-chloro-2-hexene, crotyl chloride, 1-bromo-2-butene, 2-methylallyl iodide, 1-chloro-3-ethyl-2-hexene, 3-chloro-1-butene, 2-chloro-3-pentene, 1-chloro-2-decene, 3-chlorocyclohexene, and 2-chloro-2-methyl-3-butene.

AMINE COREACTANT. An amine coreactant is required whenever the lactam synthesis is from an allylic halide precursor.
Suitable amine coreact nts inclbde ammonia and primary amines. Illustrative of the suitable primary amine co-reactants are primary amines containing one to 12 carbon atoms, including methylamine, ethylamine, n-propylamine, cyclohexylamine, benzylamine n-hexylamine and 2-ethyl-hexylamine.

IODIDE PROMOTER. Where the allylic halide precursor is an allylic chloride or bromide it is preferable to add an iodide promoter to the reaction mixture, consisting of the allylic halide substrate, amine coreactant and rhodium catalyst, prior to carbonylation~ Suitable iodide pro-moters include the alkali and alkaline earth iodides such as lithium iodide, sodium iodide, potassium iodide and calcium diiodide.

.
INERT SOLVENT. The carbonylation process of this inven-tion is most conveniently carried out in the presence of a liquid diluent. Suitable diluents may be inert organic ailuents, or they may be reactive diluents, including the aforementioned allylic halides, allylic amines and amine coreactants, or mixtures thereof. Illustrative of the normally liquid organic diluents which are generally suitable in the practice of this invention include, for example, saturated and aromatic hydrocarbons, e.g. hexane, octane, naphtha, cycloheptane, benzene, toluene, xylenes, naphthalenes, etc. N-Heterocyclic solvents such as quinoline, isoquinoline, lepidines, pyridine, etc. are also usef1~1, as weli as secondary and tertiary amines such as triethylamine and diethylamine. Nitriles such as acetonitrile and adiponitrile represent another class of suitable solvents for effecting the lactam synthesis.

TEMPERATURE. The temperature required for this carbonyla-tion process is a varia~le dependent upon experimental factors including the aIlylic precursor employed, the pressure of carbon monoxide, the concentration and natura of the rhodium catalyst, among other things. Generally an operating temperature range is from 20 to 250C when superatmospheric pressures of CO are employed.

; PRESSURE. Superatmosphere pressures of at least 10 atm.
are required for substantial conversion of allylamines to the corresponding ~-butyrolactams at temperatures of 20C and above using the rhodium catalysts of this inven-tion. Higher pre-~sures are oftentimes employed, while at pressures less than 10 atm., carbonylation is impractically slow.

', CAR~ON MONOXIDE ENVrRONMENT. Insofar as can be determined, the best selectivities and conversions to lactam can be ;
obtained within a reasonable time frame by using a sub- -stantially carbon monoxide atmosphere. However, particular-ly in continuous operations, the carbon monoxide may be used in conjunction with from 0 to about 30~ by volume of one or more inert gases such as nitrogen, argon, neon, and the like without experiencing an unacceptable decrease in yield and conversion. ;~;
, ~.

10 REACTION TIME. The time of the reaction will vary from a very short time of a few minutes or less to 24 hours or longer, depending upon the nature of the allylic substrate, the concentration and nature of the rhodium catalyst, pressure, temperature, etc. Shorter reaction times are preferred since they gi~e more economic processes.

, CONVERSION. As defined herein, conversion is the efficiency in transforming the allylic substrate to a non-allylic pro-duct. Conversion is expressed in mole percent and is calculated by dividing the amount of allylic substrate consumed during carbonylation by the amount of allylic substrate originally charged, and multiplying the quotient by 100.

YIELD. As defined herein, yield is the efficiency in catalyzing the desired carbonylation reaction relative to other undesired reaction. In this instance the forma-tion of a 5-membered ring lactam or lactam homologue is the desired reaction. Yield is usually expressed as mole .. ~... . . .

percent, and is calculated by dividing the amount of desired lactam formed by the amount of allylic halide or amine charged and multiplying the quotient obtained by 100.

IDENTIFICATIO~ PROCEDURES. Where applicable, the carbonyl-ation products of this invention are identified by one or more of the following analytical procedures, gas-liquid chromatography (glc) infrared (irl, nuclear magnetic resonance (nmr) and elemental analyses. Unless specifi'ed all percentages are by weight rather than by volume and all temperatures are in centigrade rather than fahrenheit.
- Having described the inventive process in gen-eral terms, the following examples are submitted to supply specific and illustrative embodiments.

SYNTHESIS OF~-BUTYROLACTAM FROM ALLYLAMINE
. . ~
PART A. To a degassed sample of allylamine (125 mmole) and toluene (75 ml) contained in a glass-lined reactor equipped for pressurizing, heating, cooling and means of agitation is added, under a nitrogen environment, 1.25 mmole of the rhodium salt, chlorocarbonylbis(triphenyl-phosphine)rhodium. The reactor is sealed, flusned with ~ -CO and pressured under carbon monoxide (100 atm) while heating the agitated mixture to 120C. Pressure is adjusted to 136 atm with CO and the mixture held at temperature for 2 to 12 hours. At the end of this time, carbonylation is terminated by rapid cooling and venting of the reactor. The crude product is filtered, distilled under reduced pressure (1-10 mm Hg~ to remove toluene solvent and fractionally distilled to recover the ~-butyrolactam.

, . ... . . ~

107~3396 The crude liquid product is analyzed by GLC.
Typical conversion and yield data are as foll~ws: ~

Allylamine conversion 95 mol. ~ -~-Butyrolactam yield 67 mol. %
Liquid recovery 99%

Samples of ~-butyrolactam were also recovered by preparative glc, and identified by a combination of nmr, ir, mass spec and elemental analyses.

Calcd. for C4H~NO: %C=56.5 %H=8.3 -;
Found: %C-56.6 %H=8.4 ir C=O, 1685 Cm. 1, N-H, 3240 Cm 1 lHnmr(CDC13) ~ 7.25 (s,lH), 3.42(t,2H), 2.25(t.2H), 2.13(m,2H) PART B. The synthesis`of y-butyrolactam is car-ried out substantially as described in Part A except the reaction temperature is 80C, and the reac~ion time 24 hours. ~-Butyrolactam is detected in the liquid product following completion of the carbonylation step.
PART C. The synthesis-of ~-butyrolactam is carried out substantially as described in Part A except the operating pressure of carbon monoxide is 50 atm.
Again y-butyrolactam is detected in the liquid product following completion of the carbonylation step.

" ' . . .

11~78396 , _ _ SYNTHESIS OF ~-BUTYROLACTAM FROM ALLYAMINE
USING OTHER RHODIUM CATALYSTS
_ . _ Using the same type of apparatus and techniques of Example l, ~-butyrolactam is prepared from allylamine in the presence of a variety of homogeneous and hetero-geneous rhodium catalysts. These catalysts include chlorobis(ethylenejrhodium(I) dimer, chlorotris(tri-phenylphosphine)rhodium(I), chlorocarbonylbis(triphenyl-phosphine)rhodium(I), rhodium tris(acetylacetonate~rhodium chloride and rhodium chloride in the presence of excess triphenylphosphine. Active heterogeneous rhodium catalysts include rhodium chloride and chlorocarbonyl-rhodium bonded to styrene-divinylbenzene copolymers with appended diphenylphosphine and N-cyclic groups. Table I, which summarizes the performances of said rhodium cata-lysts under the specified carbonylation conditions.
Of particular note, it may be seen from the data in Table I that 2~-butyrolactam is repeatedly synthesized here under conditions that are considerably milder than have been employed previously using the cobalt catalysts of the prior art*. In fact by comparing the yield data in Examples 2 to 4 it may be seen that the chlorobis (ethylene)rhodium(I) dimer actually gives higher yields ._ *J. ~albe and F. Korte, Chem. Ber. 98, 1928 (1965).

, ' .

- ~78396 of ~ butyrolactam at the lower carbonylation temperature `
of 150C, rather than at the temperatures normally.
employed in syntheses of the prior art (ca. 260C).
Styrene-divinylbenzene polymers are diphenyl phosphinated and treated with the homogeneous rhodium catalyst of Examples 1 to 9, and the resulting catalysts are then evaluated for carbonylation of allylamine under the conditions of Example l,.Part A. In all cases the analytical procedures, confirm the formation of the I0 desired ~ -butyrolactam product.

` ` 1078396 Table I
~-BUTYROLACTAM SYNTHESIS FROM ALLYL~INE
.
RHODIUM TEMP. PRESSURE TIME BUTYROLACTAM
EXAMPLE CATALYST (C) (atm) (hr) YIELD ~MOL~)a - 2C12[C2H4]4150 220 12 30 3 " 150 136 2 23

4 " 260 130 2 6.8 Rh(C5H72)3b 120 136 12 28 6 RhCl[PPh3]3 50 136 2 40 7 Rh(CO)Cl[PPh3]2 150 136 2 67 ~ -~
8 RhC13+2PPh3 150 190 2 22 9 RhC13 150 190 2 35 R~(CO)Cl/ 150 136 9 2 SupportC
11 RhC13/Supportd 150 136 2 16 , a ~-Butyrolactam yield based upon allyiamine charged, estimated by glc, Solvent, Toluene or2Benzene, initial [CH2=CH-CH2NH2]/[Rh]=(1-2)x10 , initial [Rh]=
10-20mM.
b Rhodium acetylacetonate c Rhodium carbonyl chloride on styrene-divinylbenzene copolymer (2~ crosslinked)with appended diphenyl-phosphine groups.
d Rhodium chloride on styrene-divinylbenzene copolymer (2~ crosslinked) with appendedgroups.

.
,;'~
,, --~.6 --,~, .

1~78396 _ _ _ _ SYNTHESIS OF ~-BUTYROLACTAM FROM ALLYLAMINE WITH
RHODIUM CATALYST RECYCLE
To a degassed sample of allylamine (125 mmole) and toluene (75 ml.) contained in a glass-lined reactor e~uipped for pressurizing, heating, cooling and means of agitation is added, under a nitrogen environment, 1.25 mmole of the rhodium salt, chlorocarbonylbis(tripher~lphosphine) rhodium. The reactor is sealed, flushed with CO and pres-10 sured under carbon monoxide (100 atm.) while heating the -agitated mixture to 120C. Pressure is adjusted to 136 atm with CO and the mixture held at temperature for 2 hours.
At the end of this time, carbonylation is terminated by rapid cooling and venting of the reactor. A small quantity (0.1 ml.) of the crude product is set aside for glc analyses, the remainder is distilled under reduced pressure (1-10 mm Hg) to remove toluene solvent and fractionally distilled ; to recover the ~-butyrolactam.
The residual catalyst solution is recharged to the glass-lined reactor with fresh toluene and allylamine.
Carbonylation is carrled out as described suPra. A third and fourth sample of allylamine are carbonylated likewise using the same catalyst solution. The results are sum-marized in Table II.
- The data serve to confirm that samples of the chlorocarbonylbis(triphenylphosphine)rhodium (I) catalyst are active for ~-butyrolactam syntheses from allylamine over at least four cycles.

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EXAMPLE_13 SYNTHESIS OF N-SUBSTITUTED-~ BUTYROLACTAM FROM ALLYL
HALI~ES _ PART A. To a degassed sample of allyl chloride (125 mmole) and acetonitrile (75 ml) contained in a glass-lined reactor equipped with pressurizing, heating, cooling and means of agitation is added, under a nitrogen environ-ment, 1.25 mmole (0.58 gm) of rhodium tris(acetylacetonate) and 4.2 gm of potassium iodide. The reactor is sealed, flushed with CO, and 8 gm of methylamine (258 mmole) is pressured in from a side ampule. The pressure is adjusted with CO to lO0 atm while the agitated mixture is heated to 120C. The pressure is further adjusted to 135 atm with CO
and the mixture held at temperature for 8 hrs. At this time the carbonylation is terminated by rapid cooling and ; venting of the reactor. A small portion (0.1 ml) of crude product is set aside for analysis, the remainder is frac-tionally distilled under reduced pressure (1-10 mm Hg) to recover the solvent and N-methyl-~ ~utyrolactam product.
Following the fractional distillation of the crude product, the residual liquid is recharged to the pressure reactor with fresh acetonitrile solvent (75 ml), allyl chlor- .
ide (125 mmole) and methylamine (8 gm, 258 mmole). Carbonyla-tion is carried out as described supra. A third sample of allyl chloride is carbonylated in a similar manner. The ; results including the lactam yield data, are summarized in Table III.
It is evident from the data summarized in this table that the rhodium acetylacetonate catalyst remains active after carbonylation and product recovery, and may be used to carbon~late additional quantities of allyl chloride to N-methyl~ butyrolactam.

-- 107839~
.

PART B. The synthesis of Part A is repeated except that cobalt octacarbonyl is substituted for rhodium tris(acetylacetonate) on a mmole-per mmole basis and the carbonylation is operated for 6 hrs at 250~C.
It is evident from the run data, summarized in Table III, that the N-methyl- -butyrolactam is prepared from allyl chloride and methylamine using the soluble rhodium catalyst in greater than ten times the yield achieved with cobalt octacarbonyl, even where the temperature employed is higher for the cobalt case.
PART C. The synthesis of Part A is repeated except that allyl bromide is substituted for~allyl ; chloride on a mmole-per-mmole basis. Analysis indicates that the desired N-methyl- ~butyrolactam is present.

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-SYNTHESIS OF ~-BUTYROLACTAM ~ROM ALLYL C~LORIDE --~

PART A. To a degassed sample of allyl chloride (125 mmole) and acetonitrile (75 ml) contained in a glass-lined reactor similar to Example I is added, under nitro-gen, 1.25 mmole (0.58 gm) of rhodium tristacetylacetono-; ate) and 4.2 gm of potassium iodide. The reactor is sealed, flushed with CO, and 10 gm of ammonia (587 mmole) is pressured in from a side ampule. The pressure is ad-justed with CO to 20 atm while the agitated mixture is heated to 120C. The pressure is further adjusted to ~ 100 atm with Cb and the mixture held at temperature for ; 8 hours. At this time the carbonylation is terminated by rapid cooling and ~enting the reactor. A small portion ~0.1 ml) of crude liquid product is set aside for analysis, the remainder is fractionally distilled under reduced pressure (1-10 mm Hg) to recover the solvent and ~-butyro-;l lactam product.
Following the fractional distillation of the crude product, the residual liquid is recharged to the pressure reactor with fresh acetonitrile solvent (75 ml), allyl chloride tl25 mmole) and ammonia (10 gm, 587 mmole).
Carbonylation is again carried out as described supra.
PART B. The synthesis of Part A is repeated ` but substituting cobalt stearate for rhodium tris(ace~yl-acetonate~ on a mmole-per-mmole basis. No ~-butyrolactam is detected by glc in the crude product solution.
PART C. The synthesis of Part A is repeated but substituting cobalt octacarbonyl fpr rhodium tris(acetyl-- 30 acetonate on a mmole-per-mmole basis. No ~-butyrolactam is detected.

SYNTHESIS OF N-~THYL~f-BUTYROLACTAM FROM ALLYL IODIDE

Using the procedure and equipment of Example 13, allyl iodide (125 mmole) and acetonitrile (75 ml) and rhodium tris(acetylacetonate) (1.25 mmole) are charged to the reactor, flushed with CO and 8 gm of methylamine injected from the side ampule. The pressure is raised with CO to 50 atm while the agitated mixture is heated to 120C.
after 8 hrs the carbonylation is terminated by rapid cooling, and venting the reactor. Analysis of the crude liquid product by glc shows the presence of N-methyl-~-butyrolactam.
As the numerous examples and preceding discussion have documented, the novel rhodium carbonylation catalysts of this invention are a significant improvement over the ;~
disclosed catalysts of the prior art, particularly regard-ing the yields of ~-lactams and their homologues, the relatively mild conditions of carbonylation employed, and the proven activity of the used rhodium catalyst samples upon recycle.
A further advantage of the instant invention is that while in some respects the process offers flexibility, ~hat lS, numerous modifications and changes can be made in the choice of catalyst and allylic substrate etc.
without departing from the inventive concept. The metes and bounds can best be determined by reading the claims which follow in light of the preceding specification.

, ,

Claims (18)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The process of preparing ?-butyrolactam or an alkyl-substituted-?-butyrolactam by the carbonylation of allylic halides having three to 10 carbon atoms, said halides selected from the group consisting of chlorides, bromides and iodides by the procedure of:
(a) Admixing said allylic halides to be carbonylated to ?-butyrolactam or an alkyl-substituted-?-butyrolactam with at least a stoichiometric amount of amine coreactant se-lected from the group consisting of ammonia and primary amines having 1 to 12 carbon, with at least a catalytic amount of rhodium catalyst selected from the group con-sisting of:
Chlorobis (ethylene) rhodium(I) dimer Chlorotris (triphenylphosphine) rhodium(I) Chlorocarbonylbis (triphenylphosphine) rhodium(I) Rhodium tris (acetylacetonate) Rhodium chloride plus triphenylphosphine and Rhodium chloride to form a reaction mixture;
(b) Pressurizing said reaction mixture with at least sufficient carbon monoxide to satisfy the stoichiometry of the carbonylation to the ?-butyrolactam or an alkyl-sub-stituted-?-butyrolactam;
(c) Heating said pressurized reaction mixture between about 20°C. and 250°C. and higher, until said allylic halide is carbonylated and ?-butyrolactam or an alkyl-substituted-?-butyrolactam is prepared, and isolating said lactams contained therein.

2. The process of claim 1 wherein the allylic halide is selected from the group consisting of an allylic chloride or an allylic bromide, and carbonylation is carried out in the presence of an alkali or alkaline earth metal iodide promoter.

3. The process of claim 2 wherein the alkali-metal iodide promoter is selected from the group consisting of lithium iodide, sodium iodide and potassium iodide.

4. The process of claim 1 wherein the primary amine coreactant is selected from the group consisting of methylamine, ethylamine and 2-ethylhexylamine.

5. The process of claim 2 in which the allylic chloride substrate is selected from the group consisting of allyl chloride, 2-methylallyl chloride and crotyl chloride.

6. The process of claim 2 in which the allylic bromide substrate is allyl bromide.

7. The process of claim 1 in which the allylic halide substrate is allyl iodide.

8. The process of claim 1 wherein the rhodium catalyst is bonded to a styrene, divinylbenzene polymer appended with diphenylphosphine donor groups.

9. The process of claim 1 wherein the lactam synthesis is carried out in the presence of an inert solvent.

10. The process of claim 9 wherein the inert solvent is selected from the group of solvents consisting of aromatic solvents, aliphatic solvents, and aliphatic nitrile solvents.

11. The process of claim 10 wherein the inert solvent is toluene.

12. The process of claim 10 wherein the inert solvent is acetonitrile.

13. The process of claim 1 wherein said rhodium catalyst is prepared in situ.

14. The process of claim 1 wherein said rhodium catalyst is preformed prior to the formation of the reaction mixture.

15. The process of claim 1 wherein the allylic halide substrate is allyl chloride, the amine coreactant is ammonia and the lactam product is ?-butyrolactam.

16. The process of claim 1 wherein the allylic halide is allyl chloride, the amine coreactant is methyl-amine and the lactam product is N-methyl-?-butyrolactam.

17. The process of preparing an alkyl-substituted--butyrolactam by the carbonylation of allylic halides having 3 to 10 carbon atoms, selected from the group con-sisting of chlorides, bromides and iodides by the procedure of:
(a) Admixing said allylic halides to be carbonylated to an alkyl-substituted-?-butyrolactam with at least a stoi-chiometric amount of an amine reactant selected from the group consisting of primary amines and secondary amines, said amines having 1 to 12 carbon atoms, with at least a catalytic amount of rhodium catalyst selected from the group consisting of:
Chlorobis (ethylene) rhodium(I) dimer Chlorotris (Triphenylphosphine) rhodium(I) Chlorocarbonylbis (triphenylphosphine) rhodium(I) Rhodium tris (acetylacetonate) and Rhodium chloride plus triphenylphosphine, said rhodium catalysts being bonded to an inert organic polymer, said inert organic polymer being selected from the group consisting of styrene, divinylbenzene polymers with appended nitrogen and phosphorus donor groups, to form a reaction mixture;
(b) Pressurizing said reaction mixture with at least sufficinet carbon monoxide to satisfy the stoichiometry of the carbonylation to an alkyl-substituted-?-butyrolactam;
(c) Heating said pressurized reaction mixture between about 20°C. and 250°C. and higher, until said allylic halide is carbonylated and an alkyl-substituted-?-butyrolactam is prepared, and isolating said alkyl-substituted-?-butyro-lactam contained therein.

18. The process of preparing ?-butyrolactam by the carbonylation of allylic chloride having three to ten carbon atoms by the procedure of:
(a) Admixing said allylic chloride to be converted to ?-butyrolactam with at least a stoichiometric amount of methylamine in the presence of iodide, with at least a catalytic amount of rhodium catalyst selected from the group consisting of:
Chlorobis (ethylene) rhodium(I) dimer Chlorotris (triphenylphosphine) rhodium(I) Chlorocarbonylbis (triphenylphosphine) rhodium(I) Rhodium tris (acetylacetonate) Rhodium chloride plus triphenylphosphine, and Rhodium chloride, said rhodium catalysts bonded to an inert organic polymer being selected from the group consisting of styrene, divinylbenzene polymers with appended nitrogen and phos-phorus donor groups, to form a reaction mixture;

(b) Pressurizing said reaction mixture with at least sufficient carbon monoxide to satisfy the stoichiometry of the carbonylation to the ?-butyrolactam;
(c) Heating said pressurized reaction mixture between about 20°C. and 250°C. and higher, until said allylic chloride is carbonylated and ?-butyrolactam is prepared, and isolating said ?-butyrolactam contained therein.