AU651239B2 - Preparation of urethane and carbonate products - Google Patents

Description

651239 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1990 REGULATION 3.2 07-21(849)A AS .9 9 49 9 9 9 9 Name of Applicant: Actual Inventor/s: Address for Service: MONSANTO COMPANY WILLIAM DENNIS McGHEE; and DENNIS PATRICK RILEY.

E.F. WELLINGTON CO., Patent and Trade Mark Attorneys, 312 St. Kilda Road, Melbourne, 3004, Victoria.

e of 9 4 9 Invention Title: "PREPARATION OF URETHANE AND CARBONATE PRODUCTS" Details of Associated Provisional Applications Nos: The following statement is a full description of this invention including the best method of performing it known to us.

1 1A 07-21(849)A BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for preparing urethanes and carbonates and, more particularly, relates to a new and useful process for preparing urethanes from amines, carbon dioxide and a hydrocarbyl halide and for preparing carbonates from alcohols, carbon dioxide and a hydrocarbyl halide. The present invention also relates to polymers prepared from such urethanes and/or carbonates.

2. Prior Art Urethanes and carbonates are typically synthesized by the reaction of a primary amine or an alcohol with phosgene to form an isocyanate or carbonate 15 salt. Thereafter, the isocyanate or carbonate is reacted with an alcohol to form the corresponding urethane or carbonate. Phosgene is very toxic and thus requires very careful handling from a product and worker safety standpoint. Isocyanates are sensitizers and are extremely toxic as well. Preparing urethane and carbonate products without using phosgene and in an economical manner, and preparing urethane products without generating isocyanates would be an achievement of considerable significance in the art.

U.S. Patent No. 4,467,089 discloses the preparation of certain carbamic acid derivatives (carbonates and carbamate esters) by the simultaneous reaction of a secondary amine and a tertiary amine with carbon dioxide to produce corresponding tertiary amine salts of N-substituted carbamic acid. The secondary and tertiary amines are brought together in equimolar proportions in the presence of excess carbon dioxide 2 07-21(849)A under mild conditions. The secondary amine reacts with

CO

2 in the presence of the tertiary amine to form the corresponding disubstituted tertiary ammonium carbamate salt. The salt is described as being useful as heat activatable delayed action catalysts, especially for use in polyurethane formulations.

Yoshida et al, Bull. Chem. Soc. Jpn., 62 1534-38 (1989) discloses preparation of urethanes from amines, carbon dioxide and alkyl halides. However, under the reaction conditions specified therein, yields of urethane product are poor as nitrogen derived products are the predominant product.

In Chemistry Express, Vol. 1, No. 4, pp 224- 227 (1986), Kinki Chemical Society, Japan, it is disclosed that primary and secondary amines absorb CO 2 to form carbamic acid amine salts and that when an equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is added, additional CO 2 is absorbed to form the DBUcarbamate salt. The DBU-carbamate salt when reacted in 20 a nonpolar aprotic solvent with an alkylating agent forms a carbamate ester (urethane). Yield and selectivity of the urethane product are highly dependent on the nature of the alkylating agent. When dibutylamine is reacted with CO 2 in the presence of DBU and the resulting DBU-carbamate salt is reacted with butyl chloride as the alkylating agent, a yield of only 17% is realized. With butyl bromide, the yield is 86%.

However, when the reaction with butyl bromide was repeated, it was observed that this yield could be achieved only if the reaction was allowed to continue for an extensive period of time, such as from about 18 to about 30 hours. Thus, this reaction, like the reaction disclosed by Yoshida et al, is not commercially S"practicable.

It has now been discovered that unexpectedly high yields can be achieved in a commercially practicable period of time, i.e. from one-fourth to onehalf of the time set forth above, by conducting the reaction in a polar aprotic solvent and in the presence of a strongly basic nitrogen-containing base selected from amidine- and guanidine-type bases.

SUMMARY OF THE INVENTION The present invention provides a triblocked carbamate compound represented by the formula: O

O

II II RI O- C-NR14- CH4 CH2)-r NRi2- C -O-RI

CH

2

I

NR13 C=0

I

0i wherein R 1 is selected from the group consisting of aralkyl and aralkenyl radicals having up to about 22 carbon atoms, and R 12

R

13 and R 14 are independently selected from the group consisting of hydrogen, and linear "or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl radicals having 1 to about 22 carbon atoms.

In preferred embodiments of the present invention

R

12

R

13 and R14 are each hydrogen, or R1 is benzyl.

In particular, the present invention provides a triblocked carbamate compound represented by the formula: 0 NH C -0O-

CH-

O (CH 2 3 CH- O- NH-CH- CH

(CH

2 4 I o NH

OCH

2 Thus, the present invention provides triblocked carbamate compounds prepared by new and useful processes for making urethanes and carbonates, as well as polyurethanes and polycarbonates. In particular, the present invention relates to a process for making urethanes and carbonates of the following general formula:

O

II

R

1

OC-A

wherein R 1 represents alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, and aralkenyl radicals having from 1 to about 22 carbon atoms, provided that R1 is not a tertiary radical of the formula (R) 3 C- or (R) 2 A represents a radical selected from the group consisting of -NR 2

R

3

NHCH(R

3 )COOH, OR 4 and 0

NR

13

C=O

I

o*U=V

O

wherein R 1

R

2 and R 3 independently represent hydrogen and alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl and alkaryl radicals having from 1 to about 22 carbon atoms, provided that not more than one of R2 and R 3 in the formula -NR 2

R

3 is hydrogen; R 4 represents alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl, alkenaryl, and alkaryl radicals having from 1 to about 22 carbon atoms; and R11 are independently selected from the group consisting of linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl radicals having 1 to about 22 carbon atoms, R 12

R

13 and R 14 are independently selected from the group consisting of hydrogen, and linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl radicals having 1 to about 22 carbon atoms, and m is an integer from 0 to 8.

R2 and R 3 together with the nitrogen may be bound to form a saturated or unsaturated heterocyclic 5 to 9 membered ring radical, such as morpholino, pyrrolidino, piperidino, and the like. In addition, one of R2 or R 3 can be 0

II

OC-0- n- 25 wherein n represents an integer of from 0 to about 8; R is as defined above, R 1 is as defined above and R represents alkylene radicals, which may be straight-chain S: or branched, having from 1 to about 22 carbon atoms, i.e., Sthe new and novel urethanes of this invention may be 30 diurethanes. Likewise, R 4 can be O R

R-N-

/II

I

A-Y R1OC-N-(-R wherein n represents an integer of from 0 to about 8; R 1 and R2 are as defined above, and R 5 represents alkylene radicals, which may be straight chain or branched, having from 1 to about 22 carbon atoms, the new and novel carbonates may be dicarbonates.

The process for preparing the subject urethanes and carbonates is characterized by reacting, in the presence of an amidine- or guanidine-type base, a suitable primary or secondary mono- or polyamine, or a suitable primary, secondary or tertiary mono-alcohol or polyol, with carbon dioxide to form the corresponding carbamate salt or carbonate salt which is then reacted with a hydrocarbyl halide. In order to achieve high yields in a reasonable period of time, the reaction between the salt and the hydrocarbyl halide is carried out in a polar aprotic solvent. Although the reaction between the amine or alcohol and carbon dioxide can be conducted in a variety of solvents, it is preferred to conduct such reaction in the polar aprotic solvent as well, primarily for convenience to avoid isolation of the salt.

The present invention is based on nucleophilic attack on the hydrocarbyl halide by carbamate anions premade from C0 2 a primary or secondary mono- or polyamine and a tertiary amine base, or by nucleophilic attack of carbonate anions pre-made from C0 2 a primary, secondary or tertiary mono-alcohol or polyol and a tertiary amine base. Urethane products made in accordance with the present invention are useful in specialty chemical applications, such as, for example, as cross-linking 30 agents. Carbonate products made in accordance with this invention are useful in preparing polymers o o 07-21(849)A which are useful in shatter-resistant optical lenses, face shields and windows.

DETAILED DESCRIPTION OF THE INVENTION The urethanes are prepared in accordance with the present invention by bringing into reactive contact a suitable primary or secondary mono- or diamine, or a mixture thereof, carbon dioxide and an amidine or guanidine base in a confined zone, such as a reactor, to prepare the corresponding ammonium carbamate salt.

Similarly, the carbonates are prepared in accordance with the present invention by bringing into reactive contact a suitable primary, secondary or tertiary monoalcohol or diol, or polyol or a mixture thereof, carbon dioxide and a base in a confined zone, such as a reactor, to prepare the corresponding carbonate salt. Preferably the amines or alcohols are in solution and the carbon dioxide is bubbled through the solution. The reaction proceeds without the need of elevated pressure or temperatures in a slightly exothermic reaction to S 20 give either the ammonium salt of the corresponding car- :bamate anion or the salt of the corresponding carbonate c anion. Use of at least an essentially stoichiometric amount of the base during the reaction with carbon **dioxide provides the desired urethane and carbonate products.

The ammonium salt of the carbamate anion is prepared in solution in the presence of the amidine-or guanidine- 0* type base. The guanidine as well as certain amidine salts of the carbamate anions are novel and represent S 30 another aspect of the present invention. The use of a base shifts the equilibrium toward the production of the carbamate anions. Where the reaction between the primary or secondary amine is carried out in the presence of a base, the reaction may be represented by the equation The resulting ammonium carbamate salt solutions are normally homogeneous.

R

2

R

3 NH Base CO 2

R

2

R

3

NCO'

2 HBase 07-21(849)A Equation shows the results of the addition of the carbamate anion to a hydrocarbyl halide.

R

2

R

3

NCO

2 HBase 1 R 1 Halide (2)

R

2

R

3

NCO

2

-R

I HBase' Halide' In order to conduct the reaction with reasonable rates and commercially practicable yields, addition of the carbamate anion to the hydrocarbyl halide is performed in a polar aprotic solvent.

Normally, the reaction, when conducted in a polar aprotic solvent, proceeds smoothly under mild conditions, e.g. at 25"C and 110 psi carbon dioxide pressure, to give the corresponding product in high yields.

Suitable primary or secondary amines used to prepare the carbamate esters in accordance with the present invention include amino acids such as glycine, aspartic acid and the like, amines represented by the following general formula:

R

2

R

3

NH,

and amines represented by the general formula: NHR4-- RiO---m R 11

NHR

12 S 25

NHR

13 wherein R 2 and R 3 independently represent hydrogen, provided that no more than one of R 2 and R 3 is hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having from 1 to about 22 carbon atoms, which radicals can be straight-chain or branched; and a radical represented by the formula 5 -)n-NHR wherein R represents radicals as defined above for R 2 R represents alkylene radicals having from about 1 to about 22 carbon atoms and n represents an integer of from 0 to about 8; Ro and R1 are independently selected from the group consisting of linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl 07-21(849)A radicals having 1 to about 22 carbon atoms, R 12

R

13 and

R

14 are independently selected from the group consisting of hydrogen, and linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl radicals having 1 to about 22 carbon atoms, and m is an integer from 0 to 8. Examples of R 2 and R 3 include methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl, phenyl, benzyl, and the like. Specific examples of such suitable amines include Nethyl(benzyl)amine, N,N-diallyamine; N,N-diethylamine; N-cyclohexylamine; N,N'-dimethylhexamethylene diamine, 4-aminomethyl-l,8-octanediamine (TAN) and the like. In addition, R 2 and R 3 together with the nitrogen can be bound to form a saturated or unsaturated 5 to 9 membered ring radical. Examples of such ring radicals include morpholino, pyrrolidino, piperidino, and the like.

Suitable amines also include polyamines such as, for example, tetraethylene pentamine, diethylene triamine, 20 triethylene tetramine and pentaethylene hexamine and the like, as well as amino acids such as alanine, arginine, asparagine, aspartic acid, cysteine, glutamine glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, t-butyl glycine, S* ornithine, norleucine and the like, including p-amino acids and homo-p-amino acids.

The amine reacts with CO 2 to reversibly form the corresponding ammonium carbamate salt. To shift the 30 equilibrium reaction more favorably to the ammonium carbamate salt, a strongly basic nitrogen-containing base is added. Such nitrogen bases include amidines DBU, 1,8-diazabicyclo[5.4.0]undec-7-ene, etc.) and guanidines cyclohexyltetramethylguanidine, cyclohexyltetraethylguanidine, and the like).

The salt of the carbonate anion can be prepared in solution in the presence of a nitrogen-containing base selected from amidines and guanidines. The guanidine as 9 07-21(849)A well as certain amidine salts of the carbonate anions are novel and represent another aspect of the present invention. The reaction between the alcohol and carbon dioxide can be represented by the equation The resulting carbonate salt solutions are normally homogeneous.

R

7 Rg 8 RCOH Base CO 2

R

7 Rs 8

RCOCO

2 HBase (3) Equation shows the results of the addition of the complex of equation 3 to a hydrocarbyl halide.

R

7

R

8

R

9 COCO0 2 HBase' R 4 Halide (4)

R

7

R

8

R

9

COCO

2

R

4 HBase+ Halide" Typically, the reaction, when conducted in a polar aprotic solvent, proceeds smoothly under mild conditions, at 25°C and 110 psi CO 2 pressure, to 20 give the corresponding product in high yield.

In one embodiment of the present invention, triblocked carbamate compounds represented by the following general formula: S 25 0 O II II RI-0-C-NR R- )m R--NR 12

-C-O-R

NR

3 1 C=0 0

R,

are prepared wherein R 1 0

R

11

R

12

R

1 3

R

1 4 and m are as defined herein. The currently preferred triblocked carbamate compounds are those based on 4-aminomethyl- 1,8-octanediamine (TAN) and represented by the general formula: 07-21(849)A 0 KIN-C-0-R1

I

H N-C-0-R i wherein R 1 is as defined herein. Specific examples of triblocked carbamate compounds based on TAN include TANtributylcarbamate where R, is butyl and TAN-tribenzylcarbamate where R 1 is benzyl.

10 Suitable primary, secondary and tertiary alcohols used to prepare the carbamate esters in 4 accordance with the present invention can be represented by the following general formula:

SR

7 yRgRCOH wherein R 7

R

8 and Rg independently represent hydrogen, .and alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl, alkenaryl and alkaryl radicals having from 1 to about 22 carbon atoms, which radicals can be 20 straight-chain or branched; a radical represented by the formula 5 -)n-OH wherein Rg and n are as defined above; or when taken together along with C form an aromatic ring structure. Examples of R 7 Rg, and R9 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, noctyl, benzyl, and the like. Specific examples of suitable alcohols include benzyl alcohol, cyclohexanol, ethanol, n-butanol, isopropanol and the like. Suitable alcohols also include diols and polyols such as, for example, ethylene glycol, sorbitol, pentaerythritol and the like.

11 07-21(849)A An advantage of the present process is that the reaction between the amine or the alcohol and CO 2 proceeds under mild temperature and pressure. Room temperature and a pressure of 110 psi CO2 are suitable and are preferred. However, if desired, the reaction can be carried out between about 25°C and about 150*C under a CO 2 pressure in a range of from about 2 psi to about 400 psi, such as from about 10 psi to about 200 psi. A preferred temperature range is from about to about 125"C, such as from about 35 0 C to about 800C.

Hydrocarbyl halides suitable for use in the present invention can be represented by the formula R 1 X wherein

R

1 represents alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl and aralkenyl radicals having from 1 to about 22 carbon atoms, provided that R, is not a tertiary radical of the formula (R) 3 C- or (R) 2 and X represents Cl, Br, I and F. Examples of such hydrocarbyl halide include alkyl, cycloalkyl, alkenyl, aralkyl halides.

Specific examples of such halides include methyl 20 chloride, methyl iodide, ethyl bromide, n-butyl bromide, n-butyl chloride, iso-butyl chloride, amyl chloride, noctyl chloride, benzyl bromide, benzyl chloride, (2naphthyl)methyl chloride, 3-chlorocyclohexene, 3- Schlorocyclohexane, 2-methyl allyl chloride, 4-chloro-2- 25 butene and the like. Hydrocarbyl dihalides and polyhalides may also be used. For example, 1,4dichloro-2-butene, 1,4-dichlorobutane, dichloro-pxylene, and the like, may be utilized. The present invention is also applicable to formation of cyclic carbamates and carbonates wherein a suitable alcohol or amine, as described above, containing a suitable leaving group such as a halide is reacted with CO 2 as set forth herein, in the presence of an amidine or guanidine base.

The reaction between the salt and the hydrocarbyl halide is carried out in a suitable polar aprotic organic solvent. As utilized herein, the phrase "polar aprotic organic Eolvent" means an aprotic organic solvent having a dielectric constant of greater than 07-21(849)A about 10e as reported in Reichardt, "Solvents and Solvent Effects in Organic Chemistry,o nd ed., VCH Verlagsgesellschaft, Weinheim, (1988), Table A-1, utilizing toluene (2.386) and tetrahydrofuran (7.58e), both at 20°C, as standards. Other methods for determining dielectric constants are known and suitable solvents are those having a dielectric constant greater than that of tetrahydrofuran utilizing any of such methods. Examples of suitable solvents include acetonitrile, N-methyl pyrrolidone, dimethylformamide, dimethylsulfoxide, and the like, as well as mixtures thereof. Preferred solvents are acetonitrile and DMSO.

Although not specifically required, it is preferred to utilize these same solvents to carry out the reaction between the amine or alcohol and carbon dioxide in order to avoid the step of isolating the salt. However, this reaction can also be conducted in other organic solvents which are not polar aprotic solvents, such as, for example, THF, methylene chloride and the like.

20 To obtain high selectivity for urethanes over amine products (oxygen vs. nitrogen attack) and high selectivity for carbonates over ethers, the anion is stabilized by the use of an essentially stoichiometric amount of a base. The term base as utilized herein refers to a base utilized in addition to the reactant amine or alcohol. This is the strongly basic nitrogencontaining base, a sterically-hindered tertiary amine base. Addition of the pre-made carbamate, or carbonate, anion under carbon dioxide pressure to a 30 solution of a hydrocarbyl halide in a suitable polar aprotic solvent gives high yields and selectivities of urethanes and carbonates and with high rates. The selection of the base in the formation of the carbamate or carbonate is important in order to obtain higher selectivities and thus higher yields. The base preferably has one of the general structures shown below.

13 07-21(849)A HR' NR'

R

2 N TR 2 R" R 2 guanidine amidine These bases are known in the art and several are commercially available. Examples of such bases include 1,5-diazabicyclo[4.3.0]non-5-ene (DBN); 1,8diazabicyclo-[5.4.0]undec-7-ene (DBU); 7-methyl-1,5,7triazabicyclo[4.4.0]dec-5-ene (MTBD); cycohexyl tetrabutyl guanidine (CyTBG) and cyclohexyl tetramethyl guanidine (CyTMG). Preferably, the molar ratio of base to the amine or alcohol starting materials will be within the range of from about 1:1 to about 10:1. A preferred molar ratio is in the range of from about 1:1 to about 1.5:1. A most preferred molar ratio is 1:1.

The rate of reaction between the carbamatr or carbonate salts and the hydrocarbyl halide can be increased by .utilizing excess, up to about 2 moles per mole of carbamate or carbonate, hydrocarbyl halide. It is believed that use of such excess hydrocarbyl halide a facilitates reaction conditions which are pseudo-first 20 order as opposed to second order. Thus, in order to render the present process more commercially practicable, it is preferred to use an excess of such hydrocarbyl halide.

It is contemplated that mixtures of alcohols and mixtures of amines can be utilized effectively in the process of the present invention. Furthermore, it is contemplated that compounds which include both alcohol and amine functional groups, diethanolamine, can be utilized effectively in the process of the present invention. In addition, it is contemplated that an alcohol/amine mixture, a mixture of N-benzyl-Nethyl amine and benzyl alcohol, can be utilized effectively in the process of the present invention. It 14 07-21(849)A is also contemplated that carbon disulfide can be utilized in place of carbon dioxide to produce the corresponding dithiocarbamates and dithiocarbonates.

Contemplated equivalents of the general formulas set forth above for the alcohols, amines and hydrocarbyl halides are compounds otherwise corresponding thereto and having the same general properties wherein one or more of the various R groups are simple variations of the substituents as defined therein, wherein R is a higher alkyl group or includes a substituent such as, for example, a halide, amino substituents, hydroxy substituents and the like. In addition, where a substituent is designated as, or can be, a hydrogen, the exact chemical nature of a substituent which is other than hydrogen at that position is not critical so long as it does not adversely affect the overall synthesis procedure. For example, where the above-specified alcohols and amines are mono- and difunctional alcohols and amines, equivalents thereof which are suitable for use in the present invention include polyols and polyamines. Where a halide is considered a leaving group, for example, as in the hydrocarbyl halide, other leaving groups such as tosyl, mesylate, triflate and the like, which are all well known in the art, are S 25 contemplated equivalents.

The chemical reactions described above are generally disclosed in terms of their broadest application to the preparation of the compounds of this invention.

Occasionally, the reactions may not be applicable as described to each compound included within the disclosed scope. The compounds for which this occurs will be readily recognized by those skilled in the art. In all such cases, either the reactions can be successfully performed by conventional modifications known to those skilled in the art, by appropriate protection of interfering groups, by changing to alternative conventional reagents, by routine modification of reaction conditions, and the like, or other reactions 07-21(849)A disclosed herein or otherwise conventional, will be applicable to the preparation of the corresponding compounds of this invention. In all preparative methods, all starting materials are known or readily preparable from known starting materials.

The invention will now be further disclosed in the following illustrated examples wherein parts and percentages are given on a molar basis unless otherwise specified.

All amines and alcohols used in the following examples were obtained either from Aldrich Chemical Company or Kodak Chemical Company and were used as received. Anhydrous solvents under nitrogen were purchased from Aldrich Chemical Co. DBN diazabicyclo[4.3.0]non-5-ene and DBU (1,8diazabicyclo[5.4.0]undec-7-ene, were also purchased from "Aldrich Chemical Co.; MTBD (7-methyl-l,5,7triazabicyclo[4.4.0]dec-5-ene was obtained from Fluka; S. CyTMG (cyclohexyl tetramethyl guanidine), as well as the 20 other cyclohexyl tetraalkyl guanidines were synthesized 0. according to the general procedure set forth in Bredereck Bredereck K. Chem Ber, 94, (1961) 2278- 2295. Thus, N-cyclohexyl-N',N',N",N"tetrabutylguanidine was synthesized according to the 25 following procedure: In a 3-1, 3-neck flask equipped with a dropping funnel, mechanical stirrer, and N 2 -bubbler, 1 mole tetrabutylurea was added and dissolved in 500 mL toluene. One mole POC1 3 was added dropwise over a minute period. The reaction was allowed to stir for 5 h at room temperature and 2.2 mole cyclohexylamine was added dropwise over a 30 minute period. The reaction was allowed to stir at room temperature for 20 h. After this period of time, the reaction was quenched with 500 mL of water. The mixture was allowed to stir vigorously for 15 minutes and then the top toluene layer was discarded. Excess solid NaOH was added to the bottom layer until two new layers were formed. The solid was 07-21(849)A filtered off and the two layers of the filtrate were separated. The bottom layer was discarded and the process was repeated with the top layer. Again, the mixture was filtered and the layers were separated. The bottom layer was discarded and the top layer was dissolved in diethyl ether. The ether solution was dried over Na 2

CO

3 filtered and concentrated. The base was purified by distillation.

Gas chromatographic analysis was performed on a Varian Model 3400 gas chromatograph with a model 8000 auto sampler using a 30 meter Megabore DB-1 (3pm) J W Scientific column. Urethane products were purified and were identified by 1H NMR, 1 C NMR, mass spectroscopy, IR, and elemental analysis. Nuclear Magnetic Resonance spectra were obtained on Varian VXR-300 or VXR-400 spectrometers. Mass spectra were obtained by FAB or by chemical ionization techniques using isobutane as Sreagent gas. Infrared spectra were obtained on a Nicolet FTIR. Molecular weight determinations of 20 polymers were obtained on GPC Waters System comprised of a WISP 700 autosampler, 600E system controller, 500A, 103A, 10 4 A and 10 5 A gel permeation columns in series, 410 Differential Refractometer and a Maxima 820 workstation.

Molecular weights are based on polystyrene standards.

25 Example 1 This example illustrates N-butyl-benzylcarbamate generation utilizing a variety of bases and demonstrates that an amidine- or guanidine-type base is required.

The bases utilized in Rxn #s 4-15 are amidine or 30 guanidine bases whereas those of Rxn #s 1-3 are not.

General procedure: A Fischer Porter bottle was charged with 1.46 g (0.02 mol) butyl amine, (0.027 mol) base, 154 mg (0.001 mol) biphenyl as internal G.C. standard, and 20 mL CH 3 CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40*C. Into a second Fischer-Porter 17 07-21(849)A bottle was added 10.12 g (0.08 mol) benzyl chloride in mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After Ih the benzyl chloride solution was added all at once under 80 psig COg to the pre-formed carbamate anion solution generated in the first Fischer- Porter bottle. After addition the reaction mixture was warmed to 55"C. Aliquots were taken periodically and were diluted with diethyl ether, Cl"'H Base filtered off, and G.C. yields calculated. The results of this study are given in Table 1.

S*

.ft *a 07-21 (849)A TABLE 1 BuNH 2 C0 2 Base

CH

3

CN

PhCH 2 C 1 BuNHC0 2

CH

2 Ph a a a a *b 1% Urethane Nitrogen Rxn Base 1 G.C. Yield derived Products 2 1 Proton Sponge 0 63 2 BuNH 2 2 77 3 PMP 7 92.5 4 n-BuTEG 45 24 t-BuDEF 48 34 6 TEG 50 17 7 TMG 62 22 8 DBU 69 18 9 MTDB 86 14 10 t-BuDMA 87 18 11 CyTEG 92 14 12 t-BuTEG 92 13 13 CyTMG 94 9 14 CyTBG 97 6 All reactions run at 550C under 80 psig carbon dioxide pressure and run to completion based on butyl amine.

30 G.C. yields determined using biphenyl as internal standard.

1 Proton Sponge N,N,N'N'-tetramethyl-1,8-naphthalenedianine. PMP 1,2,2,6, 6-pentamethylpiperadine.

N-BUTEG N-butyl-N',N',N",N"-tetraethylguanidine. t-BuDEF =N-tbutyl-N',' l-diethylformanidine.

35 TEG N,N,N',Nl-tetraethylguanidine. TMG NNN,' tetramethylguanidine. DBU 1, 8-diazabicyclo( 5.4.0 ]undec-7-ene.

MTDB =7-methyl-l,5,7-triazabicyclo(4.4.U]dec-5-ene. t-BuDMA =N-tbutyl-N' ,Nl -dimethylacetamidine.

CyTEG N-cyclohexyl-N',N',N',N"-tetraethylguanidine. t-BuTEG N- 40 t-butyl-N' ,N ,N"-tetraethylguanidine.

CyTMG N-cyclohexyl-N',N',N",N"-tetramethylguanidine. CyTEG =Ncyclohexyl-N' ,NsYtetraethylguanidine.3 CyTBG N-cyclohexyl-N' N"-tetrabutylguanidine. 3 Nitrogen derived products include, N-butyl-N-benzylamine, N-butyl-N,Ndibenzyl amine and N-butyl-N-benzyl benzylcarbamate (secondary product derived from the N-butyl-N-benzyl amine generated). A small amount of dibenzylcarbonate resulting from trace amounts of water in reagents was also detected by G.C.

a.

a..

'a a a a a a a. a.

19 07-21(849)A Example 2 This example illustrates N-butyl-benzylcarbamate generation utilizing a variety of polar aprotic solvents. General procedure: A Fischer Porter bottle was charged with 1.46 g (0.02 mol) butyl amine, (0.027 mol) base (either 1,8-diazabicyclo[5.4.0]undec-7-ene or N-cyclohexyl-N',N',N",N"-tetramethylguanidine), 154 mg (0.001 mol) biphenyl as internal G.C. standard, and mL solvent. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40'C. Into a second Fischer-Porter bottle was added 10.12 g (0.08 mol) benzyl chloride in 10 mL solvent.

This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After Ih the benzyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution S: generated in the first Fischer-Porter bottle. After 20 addition the reaction mixture was warmed to *9 9 ".Aliquots were taken periodically and were diluted with diethyl ether, Cl+H Base filtered off, and G.C. yields calculated. The results of this study are given in Table 2.

9* g. 9 07-21 (849)A TABLE 2 BuNH 2 C0 2 Solvent Base PhCH,Cl BuNHC0 2

CH

2 Ph 99 9 .9 99 9 9*9 9 9 9 9 9 0 99 99 99 9 9.

99 *999 99 .9 9 9 9 9.

9 99 .9 9 .9 9 9 99 99 Nitrogen 2 Urethane derived Rxn Base 1 Solvent 2 G.C.Yield Products 3 1 DBU N-MF 35 46 2 DBU DMF 57 8 3 DBU N-MP 59 18 4 DBU CH 3 CN 69 19 DBU Sulfolane 69 28 6 CyTMG Toluene 84 9 7 CyTMG N-MP 59 9 8 CyTMG CH 3 CN 94 9 9 CyTMG TMU 70 10 CyTMG Sulfolane 89 11 All reactions run at 55*C under 80 psig carbon dioxide pressure and run to completion based on butyl amine.

G.C. yields determined using biphenyl as internal standard. 1

DBU

1,8-diazabicyclo(5.4.0]undec-7-ene.

30 CyTMG N-cyclohexyl-N',N',N',N"-tetrametliylguanidine. 2 N-14F Nmethylformamide. DMF N,N-dimethylformamide. N-MP 1-methyl-2pyrrolidinone. TMU tetramethylurea. 3 Nitrogen derived products include, N-butyl-N-benzyl amine, N-butylN,N-dibenzyl amine and Nbutyl-N-benzyl benzylcarbamate (secondary product derived from the N-butyl-N-benzyl amine generated). A small amount of dibenzyl carbonate resulting from trace amounts of water in reagents was also detected by G.C.

21 07-21(849)A The following examples, namely Examples 3-15, illustrate a variety of urethanes prepared according to the teachings of the present invention. For comparison purposes, a summary of these examples is set forth in Table 3.

Example 3 N,N-dibutyl benzylcarbamate A Fischer Porter bottle was charged with 2.58 g (0.02 mol) dibutyl amine, 3.94 g (0.02 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine, 154 mg (0.001 mol) biphenyl as internal G.C. standard, and 20 mL CH 3 CN. The Fischer- Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a second Fischer-Porter bottle was added 10.12 g (0.08 mol) benzyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the benzyl 20 chloride solution was added all at once under 80 psig CO2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 40°C for 3h. After this time the reaction mixture was allowed to cool to room 25 temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl+HCyTMG precipitated from solution and was filtered off, and by G.C. analysis a 95% yield of urethane was calculated.

The crude material was poured into 100 mL ethyl acetate 30 and extracted with 2 x 100 mL 0.5 M aq. HC1 followed by 100 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow oil.

This oil was chromatographed on silica gel using first 100% hexane (to remove excess benzyl chloride and internal G.C. standard) and then with 100% CH 2 Cl 2 The O-benzyl carbamate product, 1, was isolated as a clear oil (3.38 g, Oil H NMR (CDC13) 6 7.39-7.30 (overlapping m, 5H), 5.17 2H), 3.27 (br, 4H), 1.55 22 07-21(849)A (br, 4H), 1.33 (br m, 4H), 0.94 (br, 6H). 13C{IH} NMR (CDC13) 6 156.7, 137.7, 128.9, 128.3, 128.2, 67.2, (47.8, 47.2), (31.4, 30.8), 20.5, 14.4. IR (film) 1703; MS (FAB) m/z 264 Anal. Calcd.: C, 72.97; H, 9.57; N, 5.32. Found: C, 73.22; H, 9.35; N, 5.45.

Example 4 N,N-diethyl benzyloarbamate Procedures as described in synthesis of 1. A G.C. yield of 95% was calculated and a 47% isolated yield of N,N-diethyl benzylcarbamate, 2 resulted. Oil. 1H NMR (CDC1 3 6 7.35-7.25 (overlapping m, 5H), 5.12 2H), 3.29 (br q, J 6.4 Hz, 4H), 1.15 J 6.9 Hz, 6H). 13C {1H} NMR (CDC13) 6 155.7, 137.1, 128.4, 127.7, 127.6, 66.7, 41.6 13.8 IR (film) 1700; MS (EI) m/z 207 Example N-butyl benzyl carbamate A Fischer Porter bottle was charged with 1.46 g (0.02 mol) butyl amine, 5.32 g (0.027 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine, 154 mg (0.001 mol) biphenyl as internal G.C. standard, and 20 mL CH 3 CN. The Fischer- Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon S. dioxide. Addition of CO2 resulted in an exothermic 25 reaction with a rise in temperature to ca. 40°C. Into a second Fischer-Porter bottle was added 10.12 g (0.08 mol) benzyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the benzyl 30 chloride solution was added all at once under 80 psig CO2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55°C for 18 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl HCyTMG precipitated from solution and was filtered off, and by G.C. analysis a 95% yield of urethane was calculated.

07-21(849)A The crude material was poured into 100 mL ethyl acetate and extracted with 2 x 100 mL 0.5 M aq. HC1 followed by 100 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow oil.

This oil was chromatographed on silica gel using first 100% hexane (to remove excess benzyl chloride and internal G.C. standard) and then with 100% CH 2 Cl 2 The 0-benzyl carbamate product, 3, was isolated as a clear oil (2.64 g, Oil. 'H NMR (CDC13) 6 7.40-7.34 (overlapping m, 5H), 5.14 2H), 4.9 (br s, 3.21 (br q, J 5.1 Hz, 2H), 1.51 2H), 1.38 2H), 0.96 J 7.2 Hz, 3H). 1C NMR (CDC13) S 156.4, 136.6, 128.4, 128.2, 127.9, 66.4, 40.7, 31.9, 19.7, 13.6. IR (film) 3337, 1701; MS m/z (MH Example 6 N-sec-butyl benzyl carbamato Procedures as described in synthesis of 3. A G.C. yield of 89% was calculated and a 44% isolated yield of N-s-butyl benzylcarbamate, 4 resulted. m.p. 49-50.5 1 H NMR 20 (CDC1 3 6 7.41-7.30 (overlapping m, 5H), 5.14 2H), 4.6 (br s, 3.69 1H), 1.50 (quintet, J 7 Hz, 2H), 1.17 J 6.6 Hz, 3H), 0.95 J 7.4 Hz, 3H).

1C H} NMR (CDC13) 6 155.8, 136.7, 128.4, 128.2, 127.9, 66.4, 48.4, 29.8, 20.7, 10.2. IR (CHC13) 34A1, 1713; MS 25 (EI) m/z 207 Anal. Calcd.: C, 69.54; H, 8.27; N, 6.76. Found: C, 69.71; H, 8.49; N, 6.87.

Example 7 S* N-tert-butyl benzyl carbamate Procedures as described in synthesis of 3. A G.C. yield of 90% was 30 calculated and a 41% isolated yield of N-t-butyl benzylcarbamate, 5 resulted. Oil. 1 H NMR (CDC13) 6 7.38-7.32 (overlapping m, 5H), 5.09 2H), 4.9 (br, N- 1.36 9H). 13 C 1 H} NMR (CDC1 3 6 155.3, 137.4, 129.0, 128.6, 128.5, 66.5, 50.8, 29.5. IR (film) 3346, 1711 (literature 1710); MS (EI) m/z 207 Anal.

Calcd.: C, 69.54; H, 8.27; N, 6.76. Found: C, 69.53; H, 8.14; N, 6.97.

07-21(849)A Example 8 N-octyl benzylcarbamate Procedures as described in synthesis of 3. A G.C. yield of 99.5% was calculated and a 53% isolated yield of N-octyl benzylcarbamate, 6 resulted after crystallization from hexane. m.p. 32-33 IH NMR (CDCl 3 6 7.41-7.29 (overlapping m, 5H), 5.08 2H), 4.77 3.17 J 6.7 Hz, 2H), 1.48 2H), 1.26 (overlapping m, 10H), 0.87 J 6.7 Hz, 3H). 13 C {1H} NMR (CDC13) 6 156.4, 136.7, 128.5, 128.1, 128.0, 66.6, 41.1, 31.8, 30.0, 29.3, 29.2, 26.7, 22.6, 14.0. IR (CHC13) 3451, 1713; MS m/z Anal.

Calcd.: C, 72.97; H, 9.57; N, 5.32. Found: C, 72.86; H, 9.51; N, 5.63.

Example 9 N-cyclohexyl benzylcarbamate Procedures as described in synthesis of 3. A G.C. yield of 97% was calculated and a 50% isola.ed yield of N-cyclohexyl benzylcarbamate, 7 resulted after crystallization from hot hexane. m.p. 93-94.5*C (literature, m.p. 93-94 C).

20 'H NMR (CDC1 3 6 7.40-7.30 (overlapping m, 5H), 5.13 (s, 2H), 4.7 (br, 3.54 1H), 1.99-1.1 (cyclohexyl, 13C NMR (CDC13) 6 155.5, 136.7, 128.5, 128.1, 128.0, 66.4, 49.9, 33.4, 25.5, 24.7. IR (CHCl 3 3441, 1711; MS (El) m/z 233 Anal. Calcd.: C, 72.07; 25 H, 8.21; N, 6.00. Found: C, 72.45; H, 8.36; N, 5.98.

Example N-cyclohexanemethyl benzylcarbamate Procedures as described in synthesis of 3. A G.C. yield of 105% was calculated and a 76% isolated yield of N- 30 cyclohexanemethyl benzylcarbamate, 8 resulted after crystallization from hot hexane. m.p. 58.5-61 C. 'H NMR (CDC13) 6 7.4-7.3 (overlapping m, 5H), 5.13 2H), 4.90 (br, 3.07 J 6.5 Hz, 2H), 1.8-0.9 (overlapping m, 11H). 13C 1 H} NMR (CDC13) 6 157.1, 137.3, 129.0, 128.6, 128.5, 67.1, 47.9, 38.8, 31.2, 26.9, 26.3. IR (CHC1 3 3455, 1713; MS m/z 248 (MH Anal. Calcd.: C, 72.84; H, 8.56; N, 5.66. Found: C, 72.84; H, 8.54; N, 5.63.

07-21(849)A Example 11 N-phenyl benzylcarbamate Procedures as described in synthesis of 3. A G.C. yield of 90% was calculated and a 64% isolated yield of N-phenyl benzylcarbamate, 9 resulted after crystallization from ether/hexane. m.p.

79-80.5 'H NMR (CDCl 3 6 7.47-7.33 (overlapping m, 8H), 7.12 J 7.3 Hz, 2H), 6.81 (br, 5.25 (s, 2H). 1C {1H} NMR (CDC13) 6 153.9, 138.3, 136.6, 129.6, 129.2, 128.9, 124.1, 119.3, 67.6. IR (CHCl 3 3435, 1734; MS (EI) m/z 227 Anal. Calcd.: C, 73.99; H, 5.77; N, 6.16. Found: C, 73.84; H, 5.80; N, 6.22.

Example 12 Tris-benzyl carbamate of N'N',N"-bis(ethylene diamine) A Fischer Porter bottle was charged with 1.03 g (0.01 mol) bis-ethylene tri-amine, 7.39 g (0.0375 mol) N-cyclohexyl-N',N',N",N"-tetramethylguanidine, and 20 mL

CH

3 CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted 20 in an exothermic reaction with a rise in temperature to :ca. 40°C. Into a second Fischer-Porter bottle was added 11.48 g (0.09 mol) benzyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After Ih 25 the benzyl chloride solution was added all at once under psig CO2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55 0 C for 18 h. After this time the reaction mixture was allowed to 30 cool to room temperature and then the pressure was released. The crude material was poured into 100 mL ethyl acetate and extracted with 2 x 100 mL 0.5 M aq.

HC1 followed by 100 mL brine. The organic layer was dried over MgSO 4 filtered and concentrated. The residue was dissolved in hexane and upon cooling A solid precipitated. After recrystallization from ethyl acetate/hexane an isolated yield of 53% (2.7 g) of the tricarbamate 10 resulted. m.p. 67-68°C. 'H NMR (CDC1 3 07-21(849)A 7.4 7.3 (overlapping m, 15H), 5.5 (br, N-H, 1H), 5.1 (br, N-H, 1H), 5.1 6H), 3.5 3.3 (overlapping br m, 8H). 13 C{jH} NMR (CDC13) 157.4, 157.3 137.1 (br), 136.8, 129.1, 129.0, 128.7, 128.6, 128.5, 68.1, 67.2, 48.3 40.5 IR (CHC13) 3451, 1711; MS (thermal spray) m/z 506 (MH Anal. Calcd.: C, 66.52; H, 6.18; N, 8.31. Found: C, 66.60; H, 6.35;, N, 8.30.

Example 13 4,4'-methylene-bis(cyclohexyl)-bis-(benzylcarbamate) A Fischer Porter bottle was charged with 2.1 g (0.01 mol) 4,4'-methylenebis(cyclohexylamine), 4.14 g (0.021 mol) N-cyclohexyl-N',N',N",N"tetramethylgua.iidine, and 20 mL 1-methyl-2-pyrrolidinone The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted :9 in an exothermic reaction with a rise in temperature to ca. 40 0 C. Into a second Fischer-Porter bottle was added 5.06 g (0.04 mol) benzyl chloride in 10 mL N-MP. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After 1h the benzyl chloride solution was added all at once under psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After 25 addition the reaction mixture was warmed to 55°C for 16 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL H 2 0 and a white precipitate formed. This white material was 30 collected by filtration and was washed with water followed by air drying at room temperature overnight giving 3.63 g of the dicarbamate 11. IR (CHC1 3 3441, 1713. Anal. Calcd.: C, 72.77; H, 8.0; N, 5.85.

Found: C, 72.79; H, 8.16; N, 5.94.

Example 14 TAN-tribenzylcarbamate A 160 cc stainless steel Parr autoclave was charged with 5.19 g (0.03 mol) 4aminomethyl-1,8-octanediamine (TAN), 17.9 g (0.096 mol) 07-21(849)A N-cyclohexyl-N',N',N",N"-tetramethylguanidine, and 30 mL 1-methyl-2-pyrrolidinone The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of

CO

2 resulted in an exothermic reaction with a rise in temperature to ca. 40"C. Into a Fischer-Porter bottle was added 22.8 g (0.18 mol) benzyl chloride. This was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the benzyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the pressure was raised again to 160 psig with carbon dioxide and the reaction mixture was warmed to 55°C for 18 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 100 mL ethyl ace. ate and extracted with 2 x 100 mL 0.5 M aq.

HC1 followed by 100 mL brine. The organic layer was 20 dried over Na 2

CO

3 filtered and concentrated. After crystallization from ethyl acetate/hexane an isolated yield of 58% (9.01 g) of the tricarbamate 12 resulted.

m.p. 78-80 1H NMR (CDC13) 6 7.4-7.34 5H), 5.1 6H), 5.1-5.0 (br, N-H, 3H), 3.2-3.05 6H), 1.6- 25 1.2 (overlapping m, 11H). C{IH} NMR (CDC1 3 6 157.4, 157.1, 137.2, 129.0, 1286, 67.2, 67.1, 44.0, 41.6, 38.6, 31.4, 30.7, 28.9, 27.3, 23.9. IR (CHC13) 3453, 1713.

Anal. Calcd.: C, 68.85; H, 7.18; N, 7.30. Found: C, 69.39; H, 7.32; N, 7.32.

30 Example Hexamethylene-1,6-bis(benzylcarbamate) A 160 cc stainless steel Parr autoclave was charged with 4.64 g (0.04 mol) 1,6-diaminohexane, 16.75 g (0.085 mol) Ncyclohexyl-N',N',N",N"-tetramethylguanidine, and 30 mL l-methyl-2-pyrrolidinone The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of

CO

2 resulted in an exothermic reaction with a rise in 07-21(849)A temperature to ca. 40*C. Into a Fischer-Porter bottle was added 20 g (0.158 mol) benzyl chloride. This was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the benzyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the pressure was raised again to 160 psig with carbon dioxide and the reaction mixture was warmed to 55*C for 18 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL H 2 0 and a white precipitate formed. This white material was collected by filtration and was washed with water followed by air drying at room temperature overnight giving 9.75 g of the dicarbamate 13. m.p. 130- 132 1H NMR (CDC13) 6 7.4-7.3 (overlapping m, 5.13 4H), 4.85 (br, N-H, 2H), 3.21 J 6.3 Hz, 4H), 1.52 (br m, 4H), 1.36 (br, 4H). 3 NMR (CDC1 3 6 157.0, 137.2, 129.0, 128.6 (overlapping), 67.1, 41.4, 30.4, 26.7. IR (CHC1 3 3453, 1713; MS (FAB) m/z 385 Anal. Calcd.: C, 68.73; H, 7.34; N, 7.29.

Found: C, 68.70; H, 7.40; N, 7.19.

0@ TABLE 3 RR'NH C0 2 CyTMG Solvent Benzyl-Cl RR NCO 2

CH

2 Ph RR 'NCH 2 Ph Urethane G.C. Yield Isolated %Amine Example RLR'NH Temp1C Solvent (Compound Yield G.C.Yield 3 Bu 2 NH 40 CH 3 CN 95(l) 64 <1 4 Et 2 NH 40 CH 3 CN 95(2) 47 <1 BuNH 2 55 CH 3 CN 95(3) 64 9 6 s-BuNH 2 55 CH 3 CN 89(4) 44 <1 7 t-BUNH 2 55 CH 3 CN 90(5) 41 <1 8 C-C 8

H

1 7

NH

2 55 CH 3 CN 99.5(6) 53 <1 9 CyNH 2 55 CH 3 CN 97(7) 50 <1 CyCH 2

NH

2 55 CH 3 CN 105(8) 76 <1 11 PhNH 2 55 CH 3 CN 90(9) 64 <1 12 (NH 2

CH

2 CH2) 2 NH 55 CH 3 CN (10) 50 13 1, 4-(NH 2 Cy) 2

CH

2 55 NMP 3 (11) 78 14 Triaminononane 2 55 NMP 3 (12)-5

H

2 N (CH 2 6

NH

2 55 NMP 3 (13) 63.5 All reactions were run under 80 psig carbon dioxide pressure and run to completion, limiting reagenisthe~ amine. An excess of benzyl chloride as used in all reactions and G.C. yields are based on biphenyl internal o standard. 1% Amine indicated by G.C. is the approximate amount of products derived from nitrogen attack on benzyl chloride. 2 Triaminononane 4.aminomethyl-1,8-octanediamine. 3 NMP l-methyl--2-pyrrolidinone.

07-21(849)A Example 16 Cbz-dibenzylaspartate A Fischer Porter bottle was charged with 2.66 g (0.02 mol) L-aspartic acid, 12.77 g (0.084 mol) 1,8-diazabicyclo[5.4.0]undec-7-ene and 25 mL

CH

3 CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40 0 C. Into a second Fischer-Porter bottle was added 15 g (0.12 mol) benzyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After Ih the benzyl chloride solution was added all at once under psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55*C for 3 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 100 mL S 20 diethyl ether and extracted with 2 x 100 mL 0.5 M aq.

HCl followed by 100 mL brine. The organic layer was dried over MgSO 4 filtered and concentrated. The excess benzyl chloride was removed by adding hexane to the crude residue leaving a light yellow oil.

Crystallization form diethyl ether/hexane gave 5.34 g of Cbz-dibenzyl aspartate 14. Product identified by NMR spectroscopy and was identical to authentic material. -1.8 (authentic material 3* Example 17 30 1,6-Hexamethylene-bis-(p-vinylbenzylcarbamate) A Fischer Porter bottle was charged with 4 g (0.035 mol) 1,6-diaminohexane, 14 g (0.092 mol) 1,8diazabicyclo[5.4.0]undec-7-ene and 30 mL CH 3 CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an -31- 07-21(849)A exothermic reaction with a rise in temperature to ca.

Into a second Fischer-Porter bottle was added g (0.13 mol) p-vinylbenzyl chloride. This was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the benzyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55°C for 4 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL 0-5 M aq. HCl giving a white solid. This solid was collected by filtration and was washed with water followed by air drying at room temperature giving 6.8 g of the dicarbamate 15. m.p. (decomposition >153 H NMR (CDC1 3 6 7.43 J 8.3 Hz, 4H), 7.34 J 8.1 Hz, 4H), 6.74 (dd, J 17.7, 10.8 Hz, 2H), 5.78 (dd, J 17.6, 0.9 Hz, 2H), 5.29 (dd, J 10.8, 0.9 Hz, 2H), 5.11 4H), 4.8 (br, N-H, 2H), 3.20 (br, 4H), 1.50 (br, 4H), 1.35 (br, 2H). 13

C{

1 H} NMR (CDC13) 6 156.9, 138.0, 136.9, 136.7, 128.9, 126.9, 114.7, 66.9, 41.4, 30.4, 26.7. IR (CHC13) 3452, 1709. Anal. Calcd.: C, 71.53; H, 7.39; N, 6.42. Found: C, 71.72; H, 7.45; N, 6.48.

Example 18 a,a'-Bis-(N,N-diethyl)-p-xylylcarbamate A Fischer Porter bottle was charged with 1.46 g (0.02 mol) diethyl amine, 3.43 g (0.022 mol) 1,8-diazabicyclo[5.4.0]undec- 7-ene and 20 mL N,N-dimethylformamide. The Fischer- 30 Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40"C. Into a second Fischer-Porter bottle was added 0.88 g (0.005 mol) a,a'-dichloro-p-xylene in 15 ml DMF. This was attached to a pressure head and 80 psig carbon dioxide -32- 07-21(849)A was added above the solution. After lh the di-chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 40"C for 21 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 100 mL diethyl ether and was then extracted with 2 x 100 mL 0.5 M aq. HC1 and 100 mL brine. The ethereal layer was dried over Na 2

CO

3 filtered and concentrated. The residue was chromatographed on silica gel using 25% ethyl acetate/hexane giving 0.96 g of the dicarbamate 16. m.p. 61-63 C. H NMR (CDC13) 5 7.36 4H), 5.14 4H), 3.31 J 6.9 Hz, 8H), 1.14 J 7.2 Hz, 12 3C{'H} NMR (CDC13) 6 156.3, 137.3, 128.3, 66.9, 0. 42 14.5 IR (CHC13) 1692; MS (thermal spray) m/z 337 (MH Anal. Calcd.; C, 64.26; H, 8.39; N, 8.33. Found: C, 64.73; H, 8.60; N, 8.36.

20 The following Examples 19-30 illustrate the present process utilizing various amines, polar aprotic solvents, hydrocarbyl halides and reaction temperatures.

A summary of these examples is set forth in Table 4.

Example 19 N,N-dibutyl butylcarbamate A Fischer-Porter bottle was charged with 2.58 g (0.02 mol) N,N-dibutyl Samine, 5.32 g (0.027 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine, 154 mg biphenyl as internal G.C.

standard and 20 mL CH 3 CN. The Fischer-Porter bottle was 30 attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of

CO

2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a second Fischer-Porter bottle was added 7.4 g (0.08 mol) butyl chloride in mL CH 3 CN. This was attached to a pressure head and psig carbon dioxide was added above the solution. After -33- 07-21(849)A lh the benzyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle.

After addition the reaction mixture was warmed to for 17.5 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with ether, solid Cl'HCyTMG filtered off and analyzed by G.C. (93.5% yield calculated). Oil. H NMR (CDCl 3 6 4.08 J 6.6 Hz, 2H), 3.21 (br, 4H), 1.65-1.3 (overlapping m, 12H), 0.95 J 7.3 Hz, 3H), 0.94 (t, J 7.3 Hz, 6H). 3C NMR (CDC13) 6 157.1, 65.3, 47.4 31.7, 31.2 20.5, 19.7, 14.4, 14.2. IR (film) 1703; MS m/z 230 (MH) Anal. Calcd.: C, 68.08; H, 11.87; N, 6.11. Found: C, 68.32; H, 10.92; N, 6.06.

Example N,N-diethyl butylcarbamate A 160 cc stainless steel Parr autoclave was charged with 2.19 g (0.03 mol) 20 diethyl amine, 8.46 g (0.043 mol) N-cyclohexyl- N',N',N",N"-tetramethylguanidine, 310 mg (0.002 mol) biphenyl as internal G.C. standard, and 25 mL CH 3 CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40"C. Into a Fischer-Porter bottle was added 8.325 g (0.09 mol) butyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above 30 the solution. After lh the butyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave.

After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 70°C for 1.5 h. After this time the reaction mixture was allowed to cool to room temperature and then the -34- 07-21(849)A pressure was released. An aliquot was taken, diluted with diethyl ether, Cl HCyTMG precipitated from solution and was filtered off, and by G.C. analysis a 97% yield of urethane was calculated. The crude material was poured into 100 mL ethyl acetate and extracted with 2 x 100 mL 0.5 M aq. HC1 followed by 100 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow residue. This was distilled and N,N-diethyl butylcarbamate was collected at 70-71°C (ca. 3 torr), 3.16 g Oil. 'H NMR (CDC13) 6 4.06 J 6.5 Hz, 2H), 3.26 J 7.1 Hz, 4H), 1.61 2H), 1.37 2H), 1.10 J 7.2 Hz, 6H), 0.93 J 7.3 Hz, 3H). 3C {1H} NMR (CDC13) 6 156.6, 65.3, 41.9, 31.7, 19.7, 14.2. IR (film) 1700; MS (thermal spray) m/z 174 Anal. Calcd.: C, 62.39; H, 11.05; N, 8.08. Found: C, 61.84; H, 10.61; N, 7.97.

Example 21 N-butyl butylcarbamate Procedures as described in synthesis of 18, using 1,8-diazabicyclo[5.4.0]undec-7ene in place of CyTMG. A G.C. yield of 82% was calculated and a 71% isolated yield of N-butyl butylcarbamate resulted after chromatography on silica gel. Oil. 1H NMR (CDC1 3 6 4.75 (br, 4.05 J 6.7 Hz, 2H), 3.15 J 6.9Hz, 2H), 1.61-1.32 (overlapping m, 8H), 0.92 J 7.31 Hz, 3H), 0.91 (t, J 7.2 Hz, 3H). 3C H} NMR (CDC13) 6 157.4, 65.1, 41.3, 32.6, 31.6, 20.4, 19.6, 14.2 (overlapping). IR (film) 3337, 1700; MS (thermal spray) m/z 174 (MH).

30 Example 22 N-phenyl butylcarbamate Procedures as described in synthesis of 18, using 1,8-diazabicyclo[5.4.0]undec- 7-ene in place of CyTMG. A G.C. yield of 67% was calculated and a 58% isolated yield of N-phenyl butylcarbamate resulted after chromatography on silica gel. m.p. 63.5-65 1H NMR (CDC13) 6 7.44 J 8 07-21(849)A Hz, 2H), 7.34 J 8 Hz, 2H), 7.09 J 7.3 Hz, 1H), 6.83 (br, 4.22 J 6.7 Hz, 2H), 1.70 (m, 2H), 1.45 2H), 1.00 J 7.3 Hz, 3H). 1C {H} NMR (CDC1 3 6 154.4, 138.6, 129.5, 123.8, 119.2, 65.6, 31.5, 19.6, 14.3. IR (CHC13) 3438, 1730; MS (FAB) m/z 194 Anal. Calcd.: C, 68.37; H, 7.82; N, 7.25.

Found: C, 68.57; H, 7.95; N, 7.29.

Example 23 4,4'-methylene-bis(cyclohexyl)-bis-(butylcarbamate) A 160 cc stainless steel Parr autoclave was charged with 3.15 g (0.03 mol) 4,4'methylenebis(cyclohexylamine), 6.9 g (0.035 mol) Ncyclohexyl-N',N',N",N"-tetramethylguanidine and 35 mL

CH

3 CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca.

40*C. Into a Fischer-Porter bottle was added 8.33 g (0.09 mol) butyl chloride in 10 mL CH 3 CN. This mixture 20 was attached to a pressure head and 80 psig carbon 9.

dioxide was added above the solution. After lh the butyl chloride solution was added all at once under psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 85°C for 6 h. After this S. time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The .crude material was poured into 100 mL ethyl acetate and 30 extracted with 2 x 100 mL 0.5 M aq. HCl followed by 100 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow residue. This was passed through a short column of silica gel using CH 2 Cl 2 as an eluent giving 5.48 g (89%) of the dibutyl carbamate 21. IR (CHC13) 3449, 1705; MS -36- 07-21(849)A m/z 411 Anal. Calcd.: C, 67.28; H, 10.31; N, 6.82. Found: C, 67.27; H, 10.09; N, 6.84.

Example 24 TAN-Tributylcarbamate A 300 cc stainless steel Parr autoclave was added 17.3 g (0.1 mol) 4-aminomethyl- 1,8-octanediamine, 60 g (0.305 mol) N-cyclohexyl- N',N',N",N"-tetramethylguanidine and 75 mL l-methyl-2pyrrolidinone The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a Fischer-Porter bottle was added 55.5 g (0.6 mol) butyl chloride. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the butyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 85°C for 18h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL ethyl acetate and extracted with 2 x 200 mL 0.5 M aq. HC1 followed by 200 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow residue. This was crystallized from ethyl acetate/hexane giving 36.5 g of the tributyl carbamate 22. m.p. 60-61 1

H

NMR (CDC1 3 6 4.85 (br, N-H, 3H), 4.05 J 6.6 Hz, 30 6H), 3.2-3.05 6H), 1.65-1.2 (overlapping m, 23H), 0.93 J 7.3 Hz, 9H). 13C{1H} NMR (CDC13) 6 157.7, 157.5, 65.2, 65.1, 44.0, 41.5, 40.9, 38.6, 31.6, 31.5, 30.8, 28.9, 27.4, 24.0, 19.6, 14.2. IR (CHC13) 3455, 1709. Anal. Calcd.: C, 60.86; H, 10.0; N, 8.87.

Found: C, 60.79; H, 10.38; N, 8.87.

-37- 07-21(849)A Example N-phenyl-2-propylcarbamate Procedures as described in synthesis of 18, using 1,8diazabicyclo[5.4.0]undec-7-ene in place of CyTMG and 2chloropropane in place of butyl chloride. A G.C. yield of 54% was calculated and a 20.5% isolated yield of Nphenyl butylcarbamate resulted after chromatography on silica gel. (A small amount of diphenyl urea was detected by G.C. in this particular reaction.) m.p.

88-89 (literature m.p. 90°C.) 'H NMR (CD 2 Cl1) 6 7.46 J 8.7 Hz, 2H), 7.35 J 8.0 Hz, 2H), 7.10 J 7.5 Hz, 1H), 6.9 (br, 5.06 (7 lines, J 6.3 Hz, 1H), 1.34 J 6.3 Hz, 6H). 13C NMR

(CD

2 C12) 6 154.2, 139.4, 129.8, 124.0, 119.5, 69.5, 22.8.

IR (CHC1 3 3437, 1728; MS (thermal spray) m/z 180 Anal. Calcd.: C, 67.02; H, 7.31; N, 7.82.

Found: C, 67.35; H, 7.45; N, 7.85.

Example 26 4,4'-methylene-bis(cyclohexyl)-bis-(2methoxyethylcarbamate) Procedures as described in synthesis of 21, using 2-chloroethyl methyl ether in place of butyl chloride. A a 70% isolated yield of the dicarbamate 24 resulted after chromatography on silica gel. IR (CHC13) 3441, 1715; MS m/z 415 (MH) Anal.

Calcd.: C, 60.85; H, 9.24; N, 6.76. Found: C, 60.68; H, 9.59; N, 6.80.

Example 27 N-Cyclohexyl allylcarbamate A Fischer Porter S. bottle was charged with 1.98 g (0.02 mol) cyclohexyl 30 amine, 5.30 g (0.027 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine, 154 mg (0.001 mol) biphenyl as internal G.C. standard, and 20 mL CH 3 CN. The Fischer- Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a -38- 07-21(849)A second Fischer-Porter bottle was added 4.6 g (0.06 mol) allyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the allyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55*C for 5 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl HCyTMG precipitated from solution and was filtered off, and by G.C. analysis a 97% yield of N-cyclohexyl allylcarbamate, 25, was calculated.

Example 28 Piperazino-bis(allylcarbamate) A Fischer Porter bottle was charged with 12.9 g (0.15 mol) piperazine, 62 g (0.41 mol) 1,8-diazabicycl[5.4.0]undec-7-ene and 90 mL N,N-dimethylformamide. The Fischer-Porter bottle was 20 attached to a pressure head and at room temperature with stirring was added 60 psig carbon dioxide. Addition of

CO

2 resulted in an exothermic reaction and cooling with ice was required. Into a second Fischer-Porter bottle was added 55 g (0.72 mol) allyl chloride in 15 mL DMF.

This mixture was attached to a pressure head and 60 psig carbon dioxide was added above the solution. After Ih the allyl chloride solution was added all at once under psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After 30 addition the reaction mixture was warmed to 50*C for 3 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 300 mL M aqueous HC1. A heavy oil settled to the bottom. This oil was collected, dissolved in 100 mL diethyl ether, dried over Na 2

CO

3 filtered and concentrated. Addition of -39- 07-21(849)A hexane followed by cooling in the freezer gave 32.8 g of the dicarbamate 26. m.p. 54-55 H NMR (CDC13) 6 5.94 2H), 5.31 (dq, J 17.2, 1.5 Hz, 2H), 5.23 (dq, J 10.3, 1.3 Hz, 2H), 4.61 (dt, 5.6, 1.3 Hz, 4H), 3.5 8H). 13 C 1 H} NMR (CDC13) 6 155.5, 133.3, 118.2, 66.8, 44.1. IR (CHC13) 1690, 1649; MS (EI) m/z 254 knal. Calcd.: C, 56.68; H, 7.13; N, 11.02.

Found: C, 56.73; H, 7.26; N, 11.03.

Example 29 4,4'-methylene-bis(cyclohexyl)-bis-(allylcarbamate) A Fischer Porter bottle was charged with 2.1 g (0.01 mol) 4,4'-methylene-bis(cyclohexylamine), 5.3 g (0.027 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine and 20 mL 1-methyl-2-pyrrolidinone.

The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction and cooling with ice was required.

Into a second Fischer-Porter bottle was added 4.6 g S 20 (0.06 mol) allyl chloride in 10 mL N-MP. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the allyl chloride solution was added a'l at once under psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55°C for h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL 30 ethyl acetate and extracted with 2 x 200 mL 0.5 M aq.

HC1 followed by 200 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow solid. This was dissolved in methylene chloride and passed through a short column of silica gel using ethyl acetate/CH 2 Cl 2 as eluent. Concentration of the filtrate gave 2.89 g of the dicarbamate 27.

07-21(849)A IR (CHC13) 3441, 1713; MS (EI) m/z 379 Anal.

Calcd.: C, 66.64; H, 9.05; N, 7.40. Found: C, 66.67; H, 9.32; N, 7.36.

Example Hexamethylene-bis-l,6-(allylcarbamate) A 160 cc Parr autoclave was charged with 4.4 g (0.038 mol) 1,6diaminohexane, 15.4 g (0.10 mol) 1,8diazabicycl[5.4.0]undec-7-ene, 403 mg tridecane as internal G.C. standard and 30 mL N,N-dimethylformamide.

The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a Fischer-Porter bottle was added 12 g (0.157 mol) allyl chloride in 20 mL DMF. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After 1h the allyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave.

S 20 After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was 'warmed to 0 C for 17.5 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, C 1HDBU filtered off, and by G.C. a 40% yield of dicarbamate was calculated. The reaction mixture was poured into 150 mL water giving a white solid. This solid was collected by filtration, washed with water and crystallized from CH 2 Cl 2 /hexane giving 30 3.52 g of the dicarbamate 28. m.p. 72.5-74 °C.

H NMR (CDC13) 6 5.92 2H), 5.31 (dq, J 17.2, 1.6 Hz, 2H), 5.21 (dq, J 10.4, 1.3 Hz, 2H), 4.89 (br, N- H, 2H), 4.56 J 5.5 Hz, 4H), 3.20 J 6.6 Hz, 4H), 1.51 4H), 1.35 4H). 13 C NMR (CDC13) 6 156.9, 133.5, 118.0, 41.3, 30.4, 26.7. IR (CHCl 3 3453, 1713, 1649; MS (EI) m/3 285 Anal. Calcd.: C, -41- 07-21(849)A 59.14; H, 8.51; N, 9.85. Found: C, 59.30; H, 8.73; N, 9.70.

1. to: 0.

S S S.

S *S* S S *SS S TABLE 4 Solvent RRINH C0 2 Base -RRRI'NCO R" R" Cl Urethane 2 Temp G. C. Yield Isolated Rxn RNH R"Cl Base 2 Solvent 3 (Compound Yield 19 Bu 2 NH Bu-Cl CyTMG 70 CH 3 CN 93.5(17) Et 2 NH Bu-Cl CyTMG 70 CH 3 CN 97(18) 61 21 BuNH 2 Bu-Cl DBU 85 CH 3 CN 82 (19) 71 21 BuNH 2 Bu-Cl CyTMG 85 CH 3 CN 73(19) 22 PhNH 2 Bu-Cl DBU 85 CH 3 CN 67 (20) 58 4 23 1, 4(NH 2 Cy) 2

CH

2 Bu-C1 DBU 85 CH 3 CN (21) 23 1, 4(NH 2 Cy) 2

CH

2 Bu-Cl CyTMG 85 CH 3 CN (21) 89 24 Triaminononanel Bu-C1 CyTMG 85 85.5 PhNH 2 i-Pr-Cl DBU 90 CH 3 CN 54(23) 20.5 26 1, 4(NH 2 Cy) 2 CH 2 MeOCH 2

CH

2 C1 CyTMG 85 CH 3 CN (24) 27 CyNH 2

CH

2

=CHCH

2 C1 CyTMG 55 CH 3 CN 97(25) 28 HN(CH 2

C

2 )NH CH =CHCH C1 DBU 50 DMF (26) 86 C 29 1, 4(NH 2 Cy) 2 CH 2

CH

2 =CHCH 2 C1 CyTMG 55 N-NP (27) 76.5

H

2 N (CH 2 6

NH

2

CH

2

=CHCH

2 Cl DBU 65 DMF 40(28) 33 TABLE 4 (Cont'd) AL 4 C *C et e Ct q.

All~ recin ru ner 8016 Ci cabo dixd prssr an aare to copein(imtn egn amin an acases ea G.C. Yields based on biphenyl as internal standard. 1 Triaminononane =4-aminomethyl-1,8-octanediamine.

2 CyTMG =N-cyclohexyl-N ,N ,N?-tetramethylguanidine. DBU 1, 8-diazabicyclo(5. 4. 0]undec-7-end.

3 N-14P 1 -methyl-2-pyrrolidinone. DUF N-dimethylformamide.

CD

0_ -44- 07-21(849)A Example 31 Butyl-1,4-bis(N,N-dibutylcarbamate) A 300 cc stainless steel Parr autoclave was charged with 32.25 g (0.25 mol) N,N-dibutyl amine, 50.2 g (0.255 mol) Ncyclohexyl-N',N',N",N"-tetramethylguanidine and 75 mL

CH

3 CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca.

40°C. Into a Fischer-Porter bottle was added 9.53 g (0.075 mol) 1,4-dichlorobutane in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the dichlorobutane solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 75 0 C for 16h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. The crude material was poured into 200 mL ethyl acetate and extracted with 2 x 200 mL 0.5 M aq. HC1 followed by 200 mL brine. The organic layer was dried over Na 2

CO

3 filtered and concentrated leaving a light yellow residue. This was chromatographed on silica gel using ethyl acetate/hexane giving 21 g of the dicarbamate 29. Oil. 'H NMR (CDC13) 6 4.1 4H), 3.2 (br m, 8H), 1.7 4H), 1.51 8H), 1.30 (sextet, J 7.4 Hz, 8H), 0.92 J 7.3 Hz, 12H). 1C{1H} NMR 6 V 30 156.8, 65.1, (47.6, 47.1), (31.3, 30.8), 26.4, 20.5, 14.3. IR (film) 1701; MS (FAB) m/z 401 (MH Anal.

Calcd.: C, 65.96; H, 11.07; N, 6.99. Found: C, 66.22; H, 11.12; N, 7.40.

Example 32 Butyl-1,4-bis(N,N-diethylcarbamate) Procedures as described in synthesis of 29, using 1,8- 07-21(849)A diazabicyclo[5.4.0]undec-7-ene in place of N-cyclohexyl- N',N',N",N"-tetramethylguanidine and N,Ndimethylformamide in place of CH 3 CN. A G.C. yield of 96.5% was calculated using biphenyl as internal standard. Oil IH NMR (CDC13) 6 4.1 4H) 3.26 J 7 Hz, 8H), 1.72 4H), 1.11 J 7.1 Hz, 12H).

13 C 1 H} NMR (CDC13) S 156.4, 65.1, 41.9, 26.4, 14.3. IR (film) 1696 (literature 1689); MS m/z Anal.

Calcd.: C, 58.31; H, 9.79; N, 9.71. Found: C, 58.30; H, 9.64; N, 9.72.

Example 33 Butyl-1,4-bis(N,N-diallylcarbamate) Procedures as described in synthesis of 29, using 1,8diazabicyclo[5.4.0]undec-7-ene in place of N-cyclohexyl- N',N',N",N"-tetramethylguanidine. Isolation by passage of the crude reaction material through silica gel using

CH

2 Cl 2 as eluent gave a 88% isolated yield of the dicarbamate 31. Oil H NMR (CDC1 3 6 5.78 4H), 5.17 (overlapping br m, 8H), 4.14 4H), 3.87 (br, 8H), 20 1.73 4H). "C {IH} NMR (CDC13) 6 156.7, 134.1, 117.0 65.5, 49.3 26.3. IR (film) 1700, 1644; MS (thermal spray) m/z 337 (MH Anal. Calcd.: C, 64.26; H, 8.39; N, 8.33. Found: C, 64.12; H, 8.62; N, 8.32.

Example 34 Butyl-1,4-bis(N-butylcarbamate) Procedures as described in synthesis of 29. A G.C. yield of 91.5% was calculated using biphenyl as internal standard. Product isolated by pouring crude reaction material into water and collecting the white solid by filtration. After washing with water and air drying a 77% isolated yield of the dicarbamate 32 resulted. m.p. 114-115 1H NMR (CDC13) 6 4.7 (br, N-H, 2H), 4.09 (br, 4H), 3.17 (br q, J 6 Hz, 4H), 1.69 (br, 4H), 1.52-1.31 (overlapping m, 8H), 0.93 J 7.2 Hz, 6H). 3C {IH} NMR (CDC13) 6 157.2, 64.8, 41.2, 32.6, 26.2, 20.4, 14.2. IR (CHC1 3 -46- 07-21(849)A 3453, 1711; MS (thermal spray) m/z 289 Anal.

Calcd.: C, 58.31; H, 9.79; N, 9.71. Found: C, 58.71; H, 10.05; N, 9.80.

Example Ethyl-1,2-bis CN,N-diethylcarbamate) Procedures as described in synthesis of 29. A G.C. yield of 85% was calculated using biphenyl as internal standard and an isolated yield of 45% of the dicarbamate 33 resulted.

Oil 'H NMR (CDCl 3 6 4.27 4H) 3.27 (br q, J 6.3 Hz, 8H) 1. 10 J 7.2 Hz, 12H) 13C {1H} NMR (CDCl 3 6 156.1, 63.8, 42.1 14.2 IR (film) 1701; MS (thermal spray) m/z =261 V"069

S

.60.5 9 s of* 00 00* a. .a TABLE Cl- (OH 2 n.-Cl 2 RR'NH +2 CO 2 2 Base RR'NCO -(CH 2 2

NR

%Di-urethane Temp. G.C.Yield Isolated Ex RR'NH Base n Solvent (0c) (Compound Yield 31 Bu 2 NH CyTMG 4 CH 3 CN 75 (29) 32 Et 2 NH DBU 4 DMF 1 70 96.5(30) 33 A1yl 2 NH DBU 4 CH 3 CN 70 (31) 88 34 BuNH 2 DBU 4 N-NP 2 85 44(32) 34 BuNH 2 CyTMG 4 N-NP 2 85 91.5(32) 77 Et 2 NH CyTMG 2 CH 3 CN 70 85(33) All reactions were run under 160 psig carbon dioxide pressure and were run to completion based on the starting dichloride.

G.C. Yields are based on biphenyl as internal standard. 1 DMF -N,N-dimethylformanide.

2 NMP =1-methyl-2--pyrrolidinone.

C.

-48- 07-21(849)A The products resulting from the abovedescribed process can be utilized to prepare polyurethanes and polycarbonates. Such products can be subjected to any one of many polymerization conditions well known in the art, depending upon the desired end use, for polyurethanes, in fibers, coatings, moulding applications and the like, and for polycarbonates, in lenses, windows, telephone parts and the like. See, for example, Mark Bikales N.; Overberger Menges Kroschwitz J. "Encyclopedia of Polymer Science and Engineering" 2nd Ed. John Wiley Sons, New York 1985, which is hereby incorporated by reference.

In addition, living polymers can be prepared 15 utilizing diamines, polyamines, diols, polyols or mixtures thereof and hydrocarbyl dihalides or hydrocarbylpoly(halides). Where it is desired to produce living polymers having a weight average molecular weight (Mw) of less than about 10,000, the reaction can be conducted utilizing any of the bases described above, such as the amidines or guanidines.

However, where it is desired to utilize the carbamates and/or carbonates of the present invention to produce a living polymer having a Mw of greater than about 10,000, 25 it is necessary to conduct the reaction in the presence of a base that will not react with the hydrocarbyl halide (which would act to terminate chain propagation of the polymerization reaction). That is, an organic nitrogenous base which is sufficiently sterically hindered such that reaction with the hydrocarbyl halide is minimized. A suitable test for determining whether a particular base is suitable, is sufficiently sterically hindered, is whether the base reacts with benzyl chloride under conditions which simulate the polymerization reaction of interest. Specific suitable bases for use in such polymerization reactions include -49- 07-21(849)A the guanidine bases as previously described. Certain amidine bases are also sufficiently sterically hindered.

An example of one of such amidines is t-butyl dimethyl acetamidine. The following Examples 36-39 illustrate preparation of polymer materials according to the teaching of the present invention.

Example 36 Oligo-urethane from piperazine, carbon dioxide and 1,4dichlorobutane (chloro terminated) A 160 cc Parr autoclave was charged with 3.44 g (0.04 mol) piperazine, 16.75 g (0.10 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine and 35 mL CH 3 CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of 15 CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40*C. Into a Fischer-Porter bottle was added 5.6 g (0.044 mol) 1,4-dichlorobutane in 10 mL

CH

3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution.

After lh the dichlorobutane solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the .0 pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 70°C for 18 h. After 25 this time the reaction mixture was allowed to cool to room temperature and then the pressure was released.

The reaction mixture was poured into 150 mL water giving a tan solid. This solid was collected by filtration, washed with water, CH 3 CN and diethyl ether (7.27 g, IR (CHC13) 1688. M 3390 by NMR end group analysis.

Example 37 Oligo-urethane from piperazine, carbon dioxide and 1,4dichlorobutane (amine terminated) A 160 cc Parr autoclave was charged with 3.44 g (0.04 mol) piperazine, 16.75 g (0.10 mol) N-cyclohexyl-N',N',N",N"tetramethylguanidine and 35 mL CH 3 CN. The autoclave was 07-21(849)A attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of

CO

2 resulted, in an exothermic reaction with a rise in temperature to ca. 40*C. Into a Fischer-Porter bottle was added 4.57 g (0.036 mol) 1,4-dichlorobutane in 10 mL

CH

3 CN. This mixture was attached to a pressure head and psig carbon dioxide was added above the solution.

After lh the dichlorobutane solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 70°C for 18 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released.

15 The reaction mixture was poured into 150 mL 0.5 M **aqueous NaOH giving a tan solid. This solid was collected by filtration, washed with water, CH 3 CN and diethyl ether (5.5 g, 1H NMR (CDC1,) 6 Oligomer backbone 4.17 3.49 1.76 Oligomer terminus 3.49 (shoulder), 2.86 IR (CHC13) 3321 1690.

Mn (NMR end group analysis) 3250.

Example 38 Chloro-terminated pre-polymer from 4,4'-methylene-bis- (cyclohexylamine), carbon dioxide and 1,4-dichlorobutane 25 10.5 g (0.05 mole) 4,4'-methylenebis(cyclohexylamine), 26.6 g (0.105 mole) N-cyclohexyl- N',N',N",N"-tetraethyl guanidine and 40 mL 1-methyl-2pyrrolidinone were added to a 160 cc stainless steel Parr autoclave. With stirring, 350-400 rpm, carbon dioxide pressure was added above the reaction mixture, 160 psig, (rxn is exothermic, temperature reached ca.

After lh 7.62 g (0.06 mole) 1,4-dichlorobutane in 10 mL N-MP was added all at once. The inlet of CO 2 was shut off and the reaction mixture was allowed to stir at 85°C for 5 h. After this time the reaction was allowed to cool to 40°C and an additional 5 g (0.039 -51- 07-21(849)A mole) 1,4-dichlorobutane was added to the reaction mixture. The reaction was heated to 85*C for 14h after which time the reaction was allowed to cool to room temperature and the pressure released. The crude reaction mixture (thick light yellow homogeneous solution) was slowly dripped into 200 ml water giving a white ppt. The ppt. was collected by filtration and washed with water, acetonitrile and finally diethyl ether. The product was dried in a vacuum oven at IR (CHC1 3 3443, 1707. M n (NMR end group analysis) 1570.

Example 39 Polyurethane from pre-polymer 36, carbon dioxide and Jeffamine-D-2000 A 300 cc stainless steel Parr 15 autoclave was charged with 10 g (0.005 mol) Jeffamine- D-2000, 3.04 g (0.012 mol) N-cyclohexyl-N',N',N",N"tetraethylguanidine, 8 g (ca. 0.005 mol) of the chloroterminated pre-polyurethane 36 and 60 mL l-methyl-2pyrrolidinone. The autoclave was attached to its pressure head and 160 psig of carbon dioxide was added above the reaction mixture After Ih the mixture was heated to 105 °C for 3 d. After this period of time the reaction was allowed to cool to room temperature and the pressure released. The thick yellow solution was slowly 25 dripped into water giving a stringy white solid. This solid was collected, washed with water and air dried.

IR (CHCI3) 3441, 1709. GPC analysis: M n 8000, M 17800, M 2.2.

Example This example illustrates the base effect on generation of polymers (polyurethanes) and demonstrates that guanidine bases must be utilized to produce polyurethanes having a Mw of about 10,000 or greater. A Fischer Porter bottle was charged with 2.1 g (0.01 mol) 4,4'methylene-bis(cyclohexylamine), 2 g (0.005 mol) Jeffamine-D-400, 5.02 g (0.0325 mol) 1,8-

I

-52- 07-21(849)A diazabicyclo[5.4.0]undec-7-ene (DBU) and 10 mL 1-methyl- 2-pyrrolidinone The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide. Addition of

CO

2 resulted in an exothermic reaction with a rise in temperature to ca. 40*C. Into a second Fischer-Porter bottle was added 2.62 g (0.015 mol) a,a'-dichloro-pxylene in 15 mL N-MP. This was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the dichloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle. After addition the reaction mixture was warmed to 55°C for 2 d. Aliquots were taken after 1 d and 2 d.

15 Each aliquot was dripped slowly into water and the solid collected by filtration, washed with water and air dried at room temperature. Molecular weight data was obtained by GPC-HPLC analysis and the results are given in Table 6. The above reaction was repeated using N-cyclohexyl-

I.

2' N',N',N",N"-tetramethylguanidine (CyTMG) and Ncyclohexyl-N',N',N",N"-tetracthylguanidine (CyTEG) in place of DBU. The results are given in Table 6. IR (CHCl 3 3441, 1709.

S

TABLE 6 mmot Jeffamin-D-400 1 C0 2 55*C Base s* 0 CPC -Pg S mmol 80 psig 33 mmol 15 nmol Rxn Base 2 Rxi Time M. M, MU/ME 1 DBU id 600 1100 1.83 2d 850 1750 2.05 2 CyTMG Id 6050 13700 2.26 2d 6350 13000 2.05 3 CyTEG Id 6800 13150 1.93 2d 7400 16300 2.2 All reactions sampled after Id and after 24 and molecular weight data was obtained by GPC-HPLC using polystyre standards. In raction 01 (DBU) only a small amount of polymer was obtained and the molecular weight data was collected on this recoverd material. In reactions #2 and 03 (CyTMG and CyTEO) good yields of recovered segmented polyurethane/polypropylene oxide resulted.

1Jeffamine-D-400 is an amine terminated polypropylene oxide of M. -400 and was obtained fmve Texaco Inc. DBU 1.8-diarabicyclo[5.4.lundec-7-ne. CyTMG N-cyclohexyl-lNf.N'.N".Ntetramethylguanidine. CyTEG N-clohexyl-N',N,N.N-ttethylgttinidine.

-54- 07-21(849)A The following Examples 41-46 illustrate preparation of carbonates according to the teachings of the present invention. For comparison purposes, these reactions are summarized in Table 7.

Example 41 Benzyl butylcarbonate A Fischer Porter bottle was charged with 1.48 g (0.02 mol) butanol, 5.3 g (0.027 mol) N-cyclohexyl-N',N',N",N"-tetramethylguanidine and mL 1-methyl-2-pyrrolidinone. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide.

Addition of CO 2 resulted in an exothermic reaction and cooling with ice was required. Into a second Fi cher- Porter bottle was added 10.12 g (0.08 mol) benzyl chlor- 15 ide in 10 mL N-MP. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the **solution. After lh the benzyl chloride solution was I added all at once under 80 psig CO 2 to the pre-formed 9. carbamate anion solution generated in the first Fischer- Porter bottle. After addition the reaction mixture was warmed to 55°C for 18h. After this time the reaction .mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, C1'HCyTMG filtered off, and by 25 G.C. analysis a 90% yield of benzyl butylcarbonate was calculated. The reaction was repeated in toluene and

CH

3 CN as solvent with the results given in Table 7. The reaction was repeated using 1,8-diazabicyclo[5.4.0]undec-7-ene in place of N-cyclohexyl-N',N',N",N"-tetramethylguanidine with CH 3 CN and toluene as solvent; the results are given in Table 7. Oil H NMR (CDC13) 7.44-7.38 (overlapping, m 5H), 5.20 2H), 4.20 J 6.7 Hz, 2H), 1.70 2H), 1.44 2H), 0.98 J 7.3 Hz, 3H). 1C{H} NMR (CDC1 3 155.8, 136.0, 129.0, 128.8, 69.9, 68.5, 31.2, 19.4, 14.2. IR (film) 1746, 1262.

07-21(849)A Example 42 Benzyl i-propylcarbonate Procedures as described in synthesis of 38. The carbonate was isolated by pouring the crude reaction mixture into diethyl ether, extracting with 2 x 100 mL 0.5 M aq. HC1 and 1 x 100 mL brine, during over NaCO0 3 filtering, concentrating and chromatography on silica gel a small amount of dibenzyl carbonate was detected and was separable from product). Oil 1H NMR (CDCI 3 7.44-7.35 (overlapping m, 5H), 5.19 2H), 4.95 (7 line pattern, J 6.3 Hz, 1H), 1.34 J 6.2 Hz, 6H). 13 C{ H} NMR (CDC1 3 155.2, 136.0, 129.1, 128.9, 128.8, 72.6, 69.7, 22.3. IR (film) 1740, 1260; MS (FAB) m/z 195 (MH).

Example 43 15 Dibenzyl carbonate Procedures as described in synthesis of 38. The carbonate was isolated by pouring the crude reaction mixture into diethyl ether, extracting with 2 x 100 mL 0.5 M aq. HC1 and 1 x 100 mL brine, during over Na 2

CO

3 filtering, concentrating and chromatography on silica gel Oil 1H NMR (CDCl 3 7.45-7.35 (overlapping m, 10H), 5.25 4H). IR (film) 1746, 1262.

Example 44 Di-ethylene glycol-bis-benzylcarbonate Procedures 25 as described in synthesis of 38. The carbonate was isolated by pouring the crude reaction mixture into diethyl ether, extracting with 2 x 100 mL 0.5 M aq. HC1 and 1 x 100 mL brine, during over Na 2

CO

3 filtering, concentrating and chromatography on silica gel Oil 'H NMR (CDC13) 7.43-7.34 (overlapping m, 10H), 5.20 4H), 4.33 4H), 3.74 4H). 3C{ H} NMR (CDC1 3 155.6, 135.7, 129.1, 129.0, 128.9, 70.2, 69.4, 67.5. IR (film) 1742, 1260; MS (FAB) m/z 375 Anal.

Calcd.: C, 64.16; H, 5.92. Found: C, 64.49; H, 6.19.

-56- 07-21(849)A Example Dibutylcarbonate A 160 cc Parr autoclave was charged with 2.22 g (0.03 mol) butanol, 6.9 g (0.035 mol) N-cyclohexyl-N',N',N",N"-tetramethylguanidine and 30 mL CH 3 CN. The autoclave was attached to a pressure head and at room temperature with stirring was added 160 psig carbon dioxide. Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca.

Into a Fischer-Porter bottle was added 8.33 g (0.09 mol) butyl chloride in 10 mL CH 3 CN. This mixture was attached to a pressure head and 80 psig carbon dioxide was added above the solution. After lh the butyl chloride solution was added all at once under 80 psig CO 2 to the pre-formed carbamate anion solution generated in the autoclave. After addition the pressure was raised to 160 psig with carbon dioxide and the reaction mixture was warmed to 85 0 C for 16 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl'-HCyTMG filtered off and by G.C. analysis a 73% yield of dibutyl carbonate was calculated. Oil 'H NMR (CDC13) 4.14(t, J 6.6 Hz, 4H), 1.66 4H), 1.41 4H), 0.94 J 7.3 Hz, 6H).

13

C{

1 H} NMR (CDCl 3 155.9, 68.2, 31.2, 19.4, 14.1. IR (film) 1746, 1260; MS (FAB) m/z 175 (MH Example 46 Di-ethylene glycol-bis-allylcarbonate A Fischer Porter bottle was charged with 1.06 g (0.01 mol) diethylene glycol, 5.3 g (0.027 mol) N-cyclohexyl-N',N',N- ",N"-tetramethylguanidine, 154 mg biphenyl as G.C. internal standard and 20 mL CH 3 CN. The Fischer-Porter bottle was attached to a pressure head and at room temperature with stirring was added 80 psig carbon dioxide.

Addition of CO 2 resulted in an exothermic reaction with a rise in temperature to ca. 40°C. Into a second Fischer- Porter bottle was added 4.6 g (0.06 mol) allyl chloride -57- 07-21(849)A in 10 mL CH 3 CN. This was attached to a pressure head and psig carbon dioxide was added above the solution.

After Ih the allyl chloride solution was added all at once under 80 psig CO2 to the pre-formed carbamate anion solution generated in the first Fischer-Porter bottle.

After addition the reaction mixture was warmed to for 14 h. After this time the reaction mixture was allowed to cool to room temperature and then the pressure was released. An aliquot was taken, diluted with diethyl ether, Cl"+HCyTMG filtered off and by G.C. analysis a yield of 84% was calculated. The crude material was poured into 100 mL diethyl ether and was then extracted with 2 x 100 mL 0.5 M aq. HC1 and 100 mL brine.

The ethereal layer was dried over Na.~3 3 filtered and 15 concentrated. The residue was chromatographed on silica S.gel using 100% hexane to remove internal standard and then CH 2 C1 2 giving 2.2 g of the di-carbonate 43.

Oil 'H NMR (CDC1 3 5.91 2H), 5.35 (dq, J 17.2, 1.4 Hz, 2H), 5.25 (dq, J 10.4, 1.4 Hz, 2H), 4.62 (dt, J 5.8, 1.4 Hz, 4H), 4.28 4H), 3.72 4H). 3C{ H} NMR (CDC13) 155.4, 132, 119.3, 69.4, 69.0, 67.3. IR (film) 1746, 1649, 1258.

S

S

S S

C

S C SS

S

S.

0 0% .S TABLE 7 R'Cl ROHl C0 2 Base ROC0 2 R Carbonate 2 Temp. G.C. Yield Isolated Ex. ROHl R'Cl Base 1 Solvent 2 (OC) (Compound Yield 41 BuQOl PhCH 2 C1 CyTMG N-lIP 55 90(38) 41 BuQOl PhCH 2 Cl CyTMG CH 3 CN 55 94(38) 41 BuQOl PhCH 2 Cl DBU CH 3 CN 55 70.5(38) 41 PhCH 2 OH BuCl CyTMG CH 3 CN 85 53(38) 42 i-PrOH PhCH 2 Cl CyTMG CH 3 CN 55 (39) 43 PhCH 2 OH PhCH 2 Cl CyTMG CH 3 CN 55 (40) 97 44 0O(CH 2

CH

2 OH) 2 PhCH 2 Cl CyTMG CH 3 CN 55 (41) 76 45 BuQOl BuCl CyTMG CH 3 CN 85 73(42) 46 0O(CH 2

CH

2 0H) 2 Ch 2

=CHCH

2 Cl CyTMG CH 3 CN 55 84(43) All reactions were run under 80-160 psig carbon dioxide pressure and carried to completion, limiting reagent= alcohol in all cases. G.C. yields determined using biphenyl as internal standard'. 1 CyTMG N-cyclohexyl- 0 N' ,N"-tetramethylguanidine. DBU 1, 8-diazabicycl[5 0]undec-7-ene. 2N-MP 1-methyl-2-pyrrolidinone.*'I' 4- -59- 07-21(849)A Example 47 This example illustrates the effect on relative rate of formation of carbamate and carbonate utilizing a polar aprotic solvent according to the teachings of the present invention as opposed to a nonpolar solvent as taught in Chemistry Express asset forth above. Thus, the rate for carbamate production in a polar aprotic solvent is increased 300% over production in a nonpolar solvent. Similarly, carbonate production in a polar aprotic solvent is increased 100% over production in a nonpolar solvent.

Into a Fischer-Porter bottle was charged 1.46 g (0.02 mol) diethyl amine, 5.3 g (0.027 mol) Ncyclohexyl-N',N',N",N"-tetramethylguanidine, 154 mg (0.001 mol) biphenyl as internal G.C. standard and 10 mL solvent (acetonitrile and toluene respectively). This was attached to a pressure head and 80 psig carbon dioxide added above the reaction mixture. Into a second Fischer-Porter bottle was added 10.12 (0.08 mol) benzyl 20 chloride in 10 mL solvent. After 1 h the chloride solution was added all at once to the diethyl carbamate anion solution under 80 psig CO, pressure. The reaction was heated to 30°C and monitored by G.C. A plot of calculated carbamic acid, benzyl ester of diethyl carbamic acid produced vs. time for reactions run in acetonitrile and in toluene are shown below.

99*9. 100 a A

A

M A A U Acwtonit* 1 A Tokno

A

0 25 50 75 100 125 150 Time (min) 07-21(849)A- Into a Fischer-Porter bottle was charged 1.48 g (0.02 mol) butanol, 5.3 g (0.027 mol) N-cyclohexyl- N',N',N",N"-tetramethylguanidine, 154 mg (0.001 mol) biphenyl as internal G.C. standard and 10 mL solvent (acetonitrile and toluene respectively). This was attached to a pressure head and 80 psig carbon dioxide added above the reaction mixture. Into a second Fischer-Porter bottle was added 10.12 (0.08 mol) benzyl chloride in 10 mL solvent. After 1 h the chloride solution was added all at once to the diethyl carbonate anion solution under 80 psig CO 2 pressure. The reaction was heated to 30°C and monitored by G.C. A plot of calculated carbonic acid, phenylmethyl ester of butyl carbonic acid, 38, produced vs. time for reactions run 15 in acetonitrile and in toluene are shown below.

GS a

S

a.

a

S

S. 5 100

A

02

A

0 100 200 300 1 M Acetonfrle A ToWne Time (min) The matter contained in each of the following claims is to be read as part of the general description of the present invention.

Claims (6)

1. A triblocked carbamate compound represented by the formula: 0 0 II II R 1 C NR 14 -(CH-f--CH 4CCH)-h NR 2 C O -R 1 CH 2 NR1 3 C=0 0 *e £5 wherein R 1 lis selected from the group consisting of aralkyl and aralkenyl radicals having up to about 22 carbon atoms, and R 12 R 13 and R14 are independently selected from the group consisting of hydrogen, and linear or branched alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, alkenaryl, alkaryl and aralkenyl radicals having 1 to about 22 carbon atoms.

2. A compound according to Claim 1 wherein R12, R 13 and R14 are each hydrogen.

3. is benzyl. A compound according to Claim 1 or 2 wherein R 1

4. A triblocked carbamate compound represented by the formula: 0 I NH C -0-CH 0 (CH2)3 CH,-O- C -NH-CH,-CH (CH2)4 H o NH -C-0-CH_, 62 A compound according to claim 1, substantially as hereinbefore described in the practical examples. DATED this 11th day of May, 1994 MONSANTO COMPANY, By its Patent Attorneys, E. F. WELLINGTON CO., eligtp A/RR/2653/9 S S S S S SS

5.55 S a S S S S S 555555

07-21(849)A ABSTRACT The present invention provides a process for preparing urethanes and carbonates from an amine or an alcohol, carbon dioxide and a hydrocarbyl halide. The amine or alcohol is reacted with carbon dioxide in a suitable solvent system and in the presence of an amidine or guanidine base, to form the ammonium carbamate or carbonate salt which is then reacted in a polar aprotic solvent with a hydrocarbyl halide. Polymer products can also be prepared utilizing this process or utilizing the resulting urethanes and carbonates under standard polymerization conditions. e