H-NMR - ACS Publications - American Chemical Society

24

Downloaded by NANYANG TECHNOLOGICAL UNIV on October 15, 2017 | http://pubs.acs.org Publication Date: June 27, 1986 | doi: 10.1021/bk-1986-0313.ch024

Investigation of the Self-Condensation of 2,4-Dimethylol-o-cresol by 1H-NMR Spectroscopy and Computer Simulation Alexander P. Mgaya1, H. James Harwood1, and Anton Sebenik2 Institute of Polymer Science, University of Akron, Akron, OH 44325 Kemijski Institute "Boris Kidric", Ljubljana, Yugoslavia

1 2

The self-condensation of 2,4-dimethylol-o-cresol in pyridine solution at 100°C was studied by 60 MHz 1H-NMR spectroscopy. Several CSMP (Continuous System Modeling Program) programs for simulating the reaction were written. One of these, when coupled with an optimization program (Chandler's STEPIT) enabled rate constants for the methylene ether forming reactions to be evaluated. The results obtained indicate that p,p-methylene ether linkages are not formed during the reaction and that the reaction occurs by nucleophilic attack of o- or p-methylol groups on o-methylol groups. This causes the condensation reaction to be much simpler than it might otherwise be expected to be.

Although the condensation of phenol with formaldehyde has been known for more than 100 years, it is only recently that the reaction could be studied in detail. Recent developments in analytical instrumentation like GC, GPC, HPLC, IR spectroscopy and NMR spectroscopy have made it possible for the intermediates involved in such reactions to be characterized and determined (1.-6). In addition, high speed computers can now be used to simulate the complicated multi-component, multi-path kinetic schemes involved in phenol-formaldehyde reactions (6-27) and optimization routines can be used in conjunction with computer-based models for phenol-formaldehyde reactions to estimate, from experimental data, reaction rates for the various processes involved. The combined use of precise analytical data and of computer-based techniques to analyze such data has been very fruitful, We previously reported a 300 MHz 1H-NMR study on the self-condensation of 2,6-dimethylol-p-cresol (27,28) (I). When the reaction conditions are sufficiently mild, this reaction yields polymer containing only methylene ether linkages. 0097-6156/86/0313-0288$06.75/0 © 1986 American Chemical Society

Provder; Computer Applications in the Polymer Laboratory ACS Symposium Series; American Chemical Society: Washington, DC, 1986.


24. MGAYA ET AL.

Self-Condensation of 2,4-Dimethylol-o-cresol

289

There i s evidence from the l i t e r a t u r e (29-33) and from our work (27,28) that t h i s reaction occurs much more e a s i l y with o-methylol groups than with p-methylol groups. This may be attributed to i n t r a molecular hydrogen bonding between a phenolic group and an adjacent o-methylol group, which could activate the l a t t e r toward nucleophilic displacement. Such activation would not be possible i n the case of p-methylol groups. To learn more about t h i s point, we have i n v e s t i gated the self-condensation of 2,4-dimethylol-o-cresol A, a compound that contains both o- and p-methylol groups.

HO

OH

OH


COMPUTER APPLICATIONS IN THE POLYMER LABORATORY

290 Experimental

2,4-Dimethylol-o-cresol, A. T h i r t y seven percent formalin solution (16.2g) was added to a solution of o-cresol (lOg) and sodium hydroxide (4g) i n 20 ml H 0 at 0°C. A f t e r standing at room temperature f o r two days the solution was brought to pH 8.2 by the addition of 10% acetic acid and c r y s t a l l i z a t i o n of 2,4-dimethylol-o-cresol began. The product was r e c r y s t a l l i z e d from chloroform to obtain white needles melting at 93-94°C ( L i t (34,35) m.p. 93-94°C). The y i e l d was 67 percent. I t i s important that very pure o-cresol be used f o r t h i s preparation; use of impure o-cresol impedes c r y s t a l l i z a t i o n of the product and i t remains i n solution, slowly forming 2,2 -dihydroxy-3,3'dihydroxymethyl-ljl'-dimethyldiphenylmethane I I , m.p. 153-155°C ( L i t m.p. 155°C (34)) i n 40 percent y i e l d . 2


1

II 1

Figure 1 shows the 60 MHz H-NMR spectrum of 2,4-dimethylol-o-cresol (2-hydroxyl-l-methyl-3,5-benzenedimethanol), A, i n pyridine at room temperature. K i n e t i c Studies. Self-condensation of A i n pyridine solution was conducted at 100°C i n 5 mm NMR tubes and the 60 MHz H-NMR spectra of the reaction mixtures were recorded at room temperature a f t e r various reaction times. The r e l a t i v e concentrations of o- and pmethylol groups and of methylene ether linkages were determined from the r e l a t i v e i n t e n s i t i e s of the resonances observed at 6=5.25 (o-methylol), 5.0 (p-methylol), 4.8-4.9 (methylene ether) and 2.3 (CH ) ppm, respectively. Resonance areas were measured by cutting and weighing expanded spectra. I n i t i a l estimates of koo were obtained by considering the reaction to be a second order process X

3



2A'DimethyloLo-cresol

Self Condensation of

MGAYA ET AL.

8.0

6.0

4.0 PPM

Figure 1.

2.0

0.0

(i )

A

60 MHz H-NMR spectrum of 2,4-dimethylol-o-cresol i n pyridine at room temperature.



292

involving only o-methylol groups. Plots of the reciprocals of the ortho methylol group concentration (Al) versus time were constructed as shown on Figure 2 and koo values were determined from the slopes of these p l o t s . The values obtained were used as i n i t i a l estimates f o r koo> kop and kpp when Chandler's STEPIT optimization program (36) was used i n conjunction with a CSMP model f o r the reaction to obtain more appropriate koo» kop and kpp values. 1


NMR Measurements. H-NMR measurements were made at room temperature using a Varian T-60 CW-NMR spectrometer. Results and Discussion X

Figure 3 shows the 60 MHz H-NMR spectra of reaction mixtures obtained by heating 2,4-dimethylol-o-cresol i n pyridine solution at 100°C f o r various periods of time. The o-methylol resonance at 5.25 ppm i s seen to decrease i n intensity, r e l a t i v e to the p-methylol resonance at 4.9 ppm, as the reaction proceeds and a new peak at 4.84.9 ppm, which i s due to methylene ether groups, increases s t e a d i l y in i n t e n s i t y . Only i n the spectrum of the reaction mixture that was heated f o r 132 hr. i s a signal due to methylene linkages evident. The chemical s h i f t of t h i s s i g n a l indicates that i t i s due to oo-type methylene linkages, based on the assignments of H i r s t e t a l . ( 5 ) . The i n t e n s i t y of t h i s signal i s weak i n t h i s instance. Since i t i s absent from most of the spectra i t can be concluded that methylene ether formation i s the predominate reaction occurring under the cond i t i o n s employed i n our studies. By comparing the intensity of the p-methylol resonance to that of o-methyl protons i t was determined that p-methylol groups are consumed i n the reaction, although at a rate considerably slower than the o-methylol groups. The o-methylol resonance region consists of at least two signals. One of these i s due to the s t a r t i n g material; the other s i g n a l , which occurs at s l i g h t l y higher f i e l d , i s t e n t a t i v e l y assigned to B2 and B3 dimers and to higher condensates. Several resonances are evident i n the methyl resonance region, but no attempt has been made to assign them. The 60 MHz H-NMR spectra of these reaction mixtures thus provide measures of the r e l a t i v e concentrations of o-methylol, p-methylol and methylene ether groups as a function of reaction time. Provided that a s a t i s f a c t o r y model i s developed f o r the condensation reaction, i t should be possible to use t h i s information to evaluate rate constants for various reactions involved. 1

A Simple Model f o r The Reaction. Several models have be*en developed for the self-condensation of A. CSMP (Continuous System Modeling Program) programming has been used to integrate numerically the set of d i f f e r e n t i a l equations associated with each model and to calculate methylol and methylene ether group concentrations as a function of time. The simplest model to assume i s based on the p o s s i b i l i t y that the r e a c t i v i t i e s of the o- and p-methylol groups are independent of the structure of the molecule to which they are attached. According to t h i s model, three rate constants koo» kop and kpp are s u f f i c i e n t to characterize the k i n e t i c behavior of the reaction at a given temperature. (The subscripts associated with these rate constants define



24.

MGAYA ET AL.


TIME IN HOURS

Figure 2.

Plot of jrj versus reaction time.


293


6 HRS 0-CH OH—1


2

P-CH OH 2

-CH OCH 2

2

24 HRS

uH. 132 HRS TMS

i i 8.0

I

I

6.0

I 4.0

i

I 2.0

l

l

0.0

PPM < © ) Figure 3.

1

60 MHz H-NMR spectra of 2,4-dimethylol-o-cresol reaction mixture i n pyridine solution at 100°C.


24.

2,4-Dimethylol-o-cresol

Self-Condensation of

MGAYA ET AL.

295

the types of methylol groups reacting; kop, f o r example denotes the rate constant f o r the reaction of an o-methylol group with a p-methy l o l group). The following d i f f e r e n t i a l equations describe the instantaneous rates of disappearance of o-methylol groups (Al) and p-methylol (A2) groups. d(Al) dt

2

= -2koo(Al) —

d(A2) - - 2 k ( A 2 ) dt

2


pp

—

k (Al)(A2) op

k (Al)(A2) op

If the i n i t i a l concentration of monomer i s C, the following equations can be solved simultaneously to obtain the concentrations of o-methylol ( A l ) , p-methylol (A2) and methylene ether (A3) groups in the reaction mixture at any time. (For s i m p l i c i t y , a methylene ether group i s considered i n t h i s c a l c u l a t i o n to contain one carbon or two hydrogens and not two carbons or four hydrogens as the correct organic structure requires).

(Al)

= C + J *

(A2) « C + £

(A3) = 2C

= C +

4i|2l

t

2

/ [ - 2 k o o ( A l ) - k p(Al)(A2)]dt 0

t

m

c

+

2

j . kpp(A2) - k (Al)(A2)]dt [

2

op

-(A1)-(A2)

Use of CSMP i n Developing the Model. Solution of these equations can be accomplished by numerical methods and i s e a s i l y done using CSMP programming. Program A l i s t s a CSMP program written to accomplish t h i s . The values of the rate constants koo(KOO), kop(KOP) and kpp (KPP) are defined i n the PARAMETER statement. The statements contained between the INITIAL and DYNAMIC statements define i n i t i a l concentrations of o-methylol (ORT), p-methylol (PAR) and methylene ether (ETHER) groups. The statements that follow the DYNAMIC statement (a), define the d i f f e r e n t i a l equations involved i n t h i s model (DORTDT*... and DPARDT=...), (b) indicate that these are to be integrated to obtain ORT and PAR, given that the i n i t i a l concentrations of these terms are equal to CONC, and (c) calculate (ETHER) as the difference between the i n i t i a l concentrations of ORT + PAR and those p r e v a i l i n g at time t . The TIMER, FINISH and PRINT statements define the output desired and how long the c a l c u l a t i o n should occur. Figure 4 shows the output of t h i s program, which consists of concent r a t i o n s of o-methylol, p-methylol and methylene ether groups at various reaction times. Although many integration routines can be used i n CSMP calculations, the variable i n t e r v a l Runge-Kutta method was used i n t h i s case since that i s the option selected when no other method i s s p e c i f i e d .



296

SIMULATION

OF 36LF-COM06NSATION O F 2t#*DIM6TMVL0L*0*CR6S0L


fine 0*0 1*00006 01 2*00006 0 1 3 * O O O O E 01 4.00006 01 9 * 0 0 0 0 6 01 9 * 0 0 0 0 6 01 7*00006 0 1 • • 0 0 0 0 6 01 9 * 0 0 0 0 6 01 t#00006 02 I • 1 0 0 0 6 02 1.20006 02 1.30006 02 1.40006 02 1 . 5 0 0 0 6 02 1.60006 02 1 . 7 0 0 0 6 02 1.60006 02 1 . 9 0 0 0 6 02 2 . 0 0 0 0 6 02 2 . 1 0 0 0 6 02 2 . 2 0 0 0 6 02 2 . 3 0 0 0 6 02 2 . 4 0 0 0 6 02 2 . 5 0 0 0 6 02 2 . 5 0 0 0 6 02 2 . 7 0 0 0 6 02 2 . 0 0 0 0 6 02 2*90006 02 3 . 0 0 0 0 6 02 3 . 1 0 0 0 6 02 3 . 2 0 0 0 6 02 3*30006 02 3 . 4 0 0 0 6 02 3 . 5 0 0 0 6 02 3 . 6 0 0 0 6 02 3 . 7 0 0 0 6 02 3 . S 0 0 0 6 02 3 . 9 0 0 0 6 02 4 . 0 0 0 0 6 02 4 . 1 0 0 0 6 02 4 . 2 0 0 0 6 02 #•30006 02 #•40006 02 #•50006 02 #•60006 02 #•70006 02 #•00006 02 #•90006 02 5*00006 02 5 . 1 0 0 0 6 02 5*20006 02 5 * 3 0 0 0 6 02 5 . 4 0 0 0 6 02 5*50006 02

OR? 1*19006 0 0 1.02916 00 9*04306-01 0*04696-01 7*23996*01 6*55916—01 9*99796*01 9*49996-01 9*07916-01 4*71006-01 #•39906-01 4*09976-01 3*04226-01 3*91206-01 3*40416-01 3*21976-01 3*04416-01 2.00716-01 2*74316-01 2*91096*01 2*49916-01 2*37496-01 2*29936-01 2*17136-01 2*07996-01 1*99436-01 1*91426-01 1*93996-01 1*79926-01 1*70196*01 1*93996-01 1*97996*01 1*92336-01 1*47016*01 1*41976*01 1*37196*01 1*32926*01 1*29296*01 1*24196*01 1*20236*01 1*19476*01 1*12996*01 1*09496*01 1*09196*01 1*03026*01 1*00006*01 9*71096*02 9*43336*02 9*19996*02 9*91066*02 9.66436-02 9*42726*02 9*19906*02 7*97926*02 7*79736*02 7*99306*02

Figure 4.

PAR 1

Bl(pp)

2koo(A)(A)

A + A

->

B2(op)

4k (A)(A)

A + A

->

B3(oo)

2k (A)(A)

A + Bl(pp)

->

Cl(op)

2k (A)(Bl)

A + Bl(pp)

->

C2(pp)

2k (A)(Bl)

A + B2(op)

->

C3(oo)

2k (A)(B2)

of A

op

pp

pp

op

pp

etc. In these expressions, a l e t t e r i s used to indicate the s i z e of the species (A=monomer, B=dimer, C^trimer, e t c . ) , a number i s used to characterize the p a r t i c u l a r species of a given s i z e and the l e t t e r s i n parentheses indicate the residual methylol f u n c t i o n a l i t y of the species. The c o e f f i c i e n t s for the rate terms were determined by the following three considerations: 1. The presence of two o- or p-methylol groups on a reactant requires a factor of two because the concentration of functional groups of that type i s twice what i t i s for reactants with both oand p-methylol groups. 2. Reactions between two i d e n t i c a l reactants require a factor of two because both species w i l l be consumed by the reaction, eg. A + A

—>

Bl

B3(oo) + B3(oo)

2koo(A)(A) 2x2x2 k o(B3)(B3) Q


24.


MGAYA ET AL.

307

3. Reactions between two reactants, each of which has one o-methylol and one p-methylol group require a factor of two because there are two ways the reaction can take place. Rate expressions f o r several reactions involving B3(oo) are given below to further i l l u s t r a t e these concepts. Rate Expressions for Disappearance of B3


Reaction B3(oo) + A

->

Cl(op)

2koo(A)(B3)

B3(oo) + A

->

C2(oo)

2k (A)(B3) op

B3(oo) + B3(oo) -> D l

8k (B3)(B3)

B3(oo) + Bl(pp) -> D4(op)

4k (Bl)(B3)

pp

op

etc.

Using reactions and rate expressions such as those written above, d i f f e r e n t i a l equations expressing the changes i n monomer and dimer concentrations with time were written as follows: 2

2

2

d(A) » -2koo(A) -2kpp(A) -2k p(A) -koo(A)(B2)-2koo(A)(B3) dt -kpp(A)(B2)-2kp (A)(Bl)-2kop(A)[(Bl)+(B2)+(B3)] 0

P

d(Bl)= dt

2

koo(A) -2k p(A)(Bl)-2kpp(A)(Bl)-8kpp(Bl)

2

0

-2k p(Bl)(B2)-2kpp(Bl)(B2)-4k p(Bl)(B3) 0

d(B2)~ dt

0

2

kop(A) -koo(A)(B2)-2k p(A)(B2)-kpp(A)(B2) 0

2

-2kop(Bl)(B2)-2k (Bl)(B2)-2koo(B2) pp

2

2

-2k p(B2) =2kpp(B2) -2koo(B2)(B3)-2k p(B2)(B3) 0

d(B3)= dt

0

2

kpp(A) -2k o(A)(B3)-2kop(A)(B3)-4kop(B3)(Bl) 0

2

-2k (B3)(B2)-2k (B2)(B3)-8koo(B3) 00

op

Simultaneous integration of these equations by numerical methods can provide the concentrations of A,B1,B2 and B3 as a funct i o n of time and the concentrations of o-methylol, p-methylol and methylene ether (note e a r l i e r d e f i n i t i o n ) groups can be calculated as follows, where CONC i s the i n i t i a l monomer concentration. (ORTHO) = (A) + (B2) + 2(B3) (PARA)

= (A) + 2(B1) + (B2)

(ETHER) = 2 CONC-(ORTHO)-(PARA)


308


Program C i s a CSMP program based on these considerations. Figure 7 shows A,Bl,B2,B3,ORTHO, PARA and ETHER concentrations calculated with the a i d of t h i s program using koo*!•5x10" M" sec- , kop 0.6xlO" ,M- ,sec- and kpp=0« Also included i n Figure 7 are experimental concentrations of o-methylol, p-methylol and methylene ether groups. Good agreement i s observed between observed and calculated r e s u l t s f o r reaction times below 50 hr., indicating the general v a l i d i t y of our approach. We w i l l now endeavor to generalize our programming to include species larger than monomer and dimers and w i l l use such programming i n more detailed studies of t h i s f a s c i nating reaction. 6


6

1

1

1

=

1

*** PROGRAM C *** TITLE SIMULATION OF SELF-CONDENSATION OF 2,4-DIMETHYLOL-o-CRESOL PARAMETER K00=0.00544,KOP«0.00212,KPP-0.0 INCON CONC-1.19 INITIAL A-CONC,B1=0.0,B2=0.0,B3*0.0,ORTHO-CONC,PARA=C0NC,ETHER=0.0 DYNAMIC DADT=-2*KOO*A*A-2*KPP*A*A-2*KOP^ . KPP*A*B2-2*KPP*A*Bl-2*KOP*A*Bl-2*KOP*A*B2-2*KOP*A*B3 DB1DT«K(X)*A*A-2*K0P*A*B1-2*KPP^ . 2*KPP*B1*B2-4*K0P*B1*B3 DB2DT=KOP*A*A-K(X}*A*B2-2*KOP^ 2*KOO*B2*B2-2*KOP*B2*B2-2*KPP*B2*B2-2*^ DB3DT«KPP*A*A-2*K(X)*A*B3-2^ . 2*KOP*B3*B2-8*KOO*B3*B3 A=INTGRL(CONC,DADT) B1=INTGRL(0.0,DB1DT) B2=INTGRL(0.0,DB2DT) B3-INTGRL(0.0,DB3DT) 0RTH0=A+B2+2*B3 PARA«A+2*B1+B2 ETHER=2*1.19-ORTHO-PARA TIMER FINTIM=1000.,DELT=1. FINISH A=3,0E-6,ORTHO=3.OE-6,PARA=3.OE-6 PRINT A,B1,B2,B3,ORTHO,PARA,ETHER END STOP ENDJOB



Figure 7.

INIEÛRAÎ10N

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RKS

ΟΗΙΜΟ ι.ιοοοε οο ι·ο3θοε οο 9.0694Ε-0Ι 0·0930ε-01 7.3007Ε-01 6.64 33Ε-01 0·0099ε-01 0.6173Ε-01 0·209ΐε-01 4·0030£-0Ι 4.5J97E-01 0.2019L-01 4.0139Ε-01 3·7912ε-0Ι 3.5902Ε-01 3·4070£-ΟΙ 3.2*10Ε-0Ι 3·0095ε-0Ι 2.9490Ε-01 2·02Ιΐε-0Ι 2.7022Ε-01 2.592ΟΕ-01 2.4695Ε-0Ι 2.3900Ε-01 2.3049Ε-0Ι 2·2210ε·0Ι 2.Ι03ΙΕ-01 2·οοοοε-οι 2.0000Ε-0Ι 1·930ΐε-01 1.0730Ε-01 ι.οιοιε-οι 1.7099ε-01 1.7075Ε-01 1.0070Ε-01 1.0100Ε-01 1.0000Ε-0Ι 1·0220ε-01 ι·%οιοε-οι ι·%%2«ε-οι |.%0S0E-01 1·3093ε-0Ι Ι.3350ε-01 Ι·3022ε-01 1·2700ε-0Ι ι·2%ο%ε-οι Ι·2113ε-01 ι·ιο3«ε-οι Ι.Ι565Ε-0Ι ι·ΐ3οοε-οι 1.1007Ε-0Ι ι·οοιοε-οι ι·οοο%ε-οι ι·ο3οιε-οι ι·οι*«ε-οι

Typical output from PRINT statement i n CSMP programs·

SIMULAIION OF SELF-CONOENSAIION OF 2.4-OIMEtHVLOL-O-CRE SOL 02 03 81 A tine 0*0 1.1900E 00 0.0 0.0 0.0 Ι·ΟΟΟΟΕ 01 1.0060E 00 4.3629Ε-02 2.40Ι3Ε-02 0.0 2·OOOOE 01 0.0759E-0I Ι.0760Ε-01 3.035lt-02 0 .0 3.OOOOE 01 7.0007E-01 1.3900Ε-0Ι 4.9296Ε-02 0 .0 4.0000E 01 0·743ΐε-01 Ι.0190Ε-01 5.5750Ε-02 0..0 9.0000E 01 ο·θ44*ε-οι 1.7912Ε-01 5.909JE-02 0 .0 ο·οοοοε οι 0·4090ε-0Ι 1.9209Ε-01 6.244ΙΕ-02 0.0 7·0000Ε 01 4.9704Ε-01 2.0200Ε-01 0.3000Ε-02 0 >0 0·OOOOE 01 4.56J6E-0I 2.0964Ε-01 6.4553Ε-02 0 .0 9·OOOOE 01 4·2003ε-01 2·1506Ε-01 6.4667Ε-02 0.»0 I·OOOOE 02 3.0990Ε-01 2.2014Ε-01 0.4300Ε-02 0 • 0 1·1OOOE 02 J.6236E-01 2.2360Ε-01 0.3022Ε-02 0 • 0 I.2000E 02 3.3033Ε-01 2.2640Ε-0Ι 0.30S0E-02 0.»0 1.3000E 02 3.1097Ε-01 2·2047Ε·01 6.2Ι49Ε-02 0.• 0 |.»000E 02 2.9707Ε-01 2.3002Ε-01 6.Ι143Ε-02 0..0 1·OOOOE 02 2.0070Ε-01 2.31ΙΟΕ-ΟΙ 6.0Θ7ΙΕ-92 0 »0 1·OOOOE 02 2.6520Ε-0Ι 2.3194Ε-0Ι 9·090θε-02 0..0 I.7000C 02 2.0113Ε-0Ι 2.3249Ε-0Ι 5.702ΙΕ-02 0..0 1·OOOOE 02 2·303ΐε-01 2.3273Ε-01 5.6674Ε-02 0,,0 1·OOOOE 02 2.2609Ε-01 2.3202Ε-01 0·0027ε-02 0,»0 2.0000E 02 2.1503Ε-0Ι 2 · 32 79Ε-01 5.4300Ε-02 0.0 2·1OOOE 02 2.0093Ε-0Ι 2.3256Ε-0Ι 5.3263Ε-02 0.,0 «•2OOOE 02 Ι.9679Ε-0Ι 2.3226Ε-01 0.2Ι00Ε-02 0.0 2.3000E 02 L0033E-01 2.3100Ε-01 9.1009Ε-02 0« 0 2·4OOOE 02 1.0040Ε-0Ι 2.3Ι42Ε-0Ι Ο.ΟΟΟΟΕ-02 0« 0 2·OOOOE 02 1.7310Ε-01 2.3090Ε-01 0.0900Ε-02 0.0 2·OOOOE 02 Ι.6636Ε-0Ι 2.3034Ε-0Ι 0·7902ε-02 0,0 2.7000E 02 1·0000Ε-01 2.2973Ε-0Ι 0.0903ε-02 0.0 2·OOOOE 02 I.SOOOE-OI 2.2909Ε-0Ι ο.οοοοε-02 0,0 2·OOOOE 02 Ι.4045Ε-0Ι 2.2043Ε-01 ο.οοοοε-02 0.0 9·OOOOE 02 Ι.4 3Ι9Ε-01 2.2774Ε-0Ι 4.415JE-02 0.0 9*1OOOE 02 Ι.3025Ε-01 2.2704Ε-01 4.3267Ε-02 0« 0 3,2OOOE 02 1.3309Ε-0Ι 2·2033Ε·01 4.2406Ε-02 0,0 9·9000Ε 02 1.2910Ε-01 2.2561Ε-01 4.1569Ε-02 0.0 3.4000C 02 Ι.2902Ε-01 2.2400Ε-01 4.0700Ε-02 0,0 3.0000E 02 1.210ΟΕ-0Ι 2.2014Ε-01 3.9900Ε-02 0.0 9·OOOOE 02 ι·ΐ73οε-οι 2.2341Ε-01 3.9197Ε-02 0..0 3.7000E 02 ι·ΐ3οοε-οι 2.22οοε-οι 3.6451Ε-02 0«>0 9·OOOOE 02 Ι.1043Ε-0Ι 2.2195Ε-01 3.7726Ε-02 0..0 J.OOOOE 02 Ι.0722Ε-0Ι 2.2122Ε-0Ι 3·702ΐε-02 0,,0 0·OOOOE 02 1.04Ι7Ε-01 2.2049Ε-01 3.0330Ε-02 0«,0 0*1OOOE 02 1.0Ι26Ε-01 2.1977Ε-0Ι 3.5670Ε-02 0,.0 0*2OOOE 02 9.04 70£-02 2.1905Ε-0Ι 3.0022Ε-02 0,.0 4·3OOOE 02 9.S024E-02 2.16J5E-0I 3.4J9IE-02 0,,0 0·OOOOE 02 9.3200Ε-02 2.Ι764Ε-01 3.3770Ε-02 0,.0 4·OOOOE 02 9.0090Ε-02 2.1090Ε-01 3.3102Ε-02 0,.0 0.OOOOE 02 0.0933Ε-02 2.Ι626Ε-01 3.2601Ε-02 0..0 4.7000E 02 0.6304Ε-02 2.1550Ε-01 3.2030Ε-02 0.»0 «•ooooe 02 β·οιοοε-ο2 2.Ι491Ε-0Ι 3.1405Ε-02 0,.0 %.ooooe 02 0.21Ι3Ε-02 2.1424Ε-0Ι 3.0909Ε-02 0.,0 ••OOOOE 02 0.0141Ε-02 2.1309Ε-01 3.0427Ε-02 0,»0 0*1OOOE 02 7.0246Ε-02 2.1294Ε-01 2·9910ε-02 0..0 0.2000E 02 7.6422Ε-02 2.1230Ε-01 2·9%22Ε-02 0,.0 0.3000Ε 02 7.4ΟΟ7Ε-02 2.1107Ε-01 2.0939ε-02 0 .0 «•OOOOE 02 7.2970Ε-02 2.1Ι05Ε-01 2·0%0θε-02 0,»0


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310


Conclusion


By simultaneously using NMR spectroscopy and computer simulation to study the self-condensation of 2,4-dimethylol-o-cresol, evidence has been obtained that only ortho methylol groups i n t h i s compound and i t s analogous higher condensates are a c t i v a t e d toward reaction with n u c l e o p h i l i c reagents. As a r e s u l t of t h i s , no p,p-methylene ether linkages are formed i n t h i s reaction and i t i s much simpler than i t might otherwise be. CSMP programming i s very valuable f o r studies of t h i s general nature and i t s u t i l i z a t i o n i s r e l a t i v e l y simple. Acknowledgments This work was supportd i n part by a grant from the National Science Foundation (DMR-83-03739). Literature Cited

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20.

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24.MGAYAETAL.


311

21. Sebenik, A.; Lapanje, S. Angew. Makromol. Chem., 63, 139 (1977) 22. Borrajo, J . ; Arangeren. M. I.; Williams, R. J. J. Polymer, 23, 263 (1982). 23. Frontini, P. M.; Cuadrado, T. R.; Williams, R. J. J. Polymer, 23, 267 (1982). 24. Zavitsas, A. A.; Beaulieu, R. D.; Leblanc, J. R. J. Polym. Sci., Al, 6, 2541 (1968). 25. Steffan, R. Angew. Makromol. Chem., 131, 25 (1985). 26. Harwood, H. J.; Dworak, A.; Nyeu, T. K.; Tong, S. N. A.C.S. Symposium Series, 45, 220 (1981). 27. Tong, S. N.; Park, K. Y.; Harwood, H. J. Polymer Preprints, 24(2), 196 (1983). 28. Tong, S. N.; Park, K. Y.; Harwood, H. J. J. Polym. Sci., Polym. Chem. Ed., 22, 1097 (1984). 29. Megson, N. J. L. Phenolic Resin Chemistry, Academic, New York, 1958, Chap. III. 30. Hultzsch, K. Chemie der Phenolharze, Springer-Verlag, Heidelberg, 1950, Chap. III. 31. Kammerer, H. Kunstoffe, 56, 154 (1966). 32. Kammerer, H.; Grossman, M.; Umsonst, G. Makromol. Chem., 39, 39 (1960). 33. Kammerer, H.; Muck, K. F.; Golzer, E.; Luder, H. Makromol. Chem., 138, 119 (1970). 34. Granger, F. S. Ind. Eng. Chem., 24, 443 (1932). 35. Barclay, M. G.; Buraway, A.; Thomson, G. H. J. Chem. Soc., 400 (1944). 36. Chandler, J. P. Subroutine STEPIT Program 66.1, Quantum Chemistry Program Exchange, Indiana University, Bloomington, Indiana. RECEIVED March 10, 1986


H-NMR - ACS Publications - American Chemical Society

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