MARCH1967
603
CY-HALOPERFLUOROMETHY L-S-TRIAZINES
The Preparation and Coupling of Some a-Haloperfiuoromethyl-s-triazines’ G. A. GRINDAHL, W. X. BAJZER,AND 0. R. PIERCE Fluorine Research Laboratories, DOZO Corning Corporatim, Midland, Michigan 48640 Received September SO, 1966
A variety of a-haloperfluoromethyl-s-triazines was used in a study of mercury-induced coupling reactions. Qualitatively, the order of reactivity of the a-halo atom is Br > C1 > F. a-Bromo is sufficiently reactive to allow the preparation of a linear poly(perfluoroalkylperfluoroalky1ene-s-triazine)from 2,4-bis(bromodifluoromethyl)-6-trifluoromethyl-1,3,5-triazine. The new nitriles, CFzBrCN and CFdCN, and the new anhydride, (CFZBrCO)zO, were prepared via specially developed routes. From these, several new substituted triazines were obtained by modification of available techniques.
Poly(perfluoroalky1enetriazines) were first prepared by Brown2 by thermal deammonation of perfluoroalkyleneamidine~.~The resulting polymers were of interest owing to their high degree of thermal and chemical stability. However, the random nature of the formation of the triazine ring precluded any great degree of linearity in the polymer structure. More recently, Dorfman, et aZ.,* described a procedure in which a poly(imidoy1amidine) was first formed from an a,w-fluorocarbon dinitrile followed by acylation and ring closure using a fluorocarbon acid anhydride to give the triazine structure. A much greater degree of polymer linearity was achieved. To avoid uncontrolled triazine formation and rearrangement during condensation polymerization, and the undesirable cross-linking that resulted, it seemed advantageous to prepare and isolate pure samples of difunctional triazine compounds which could be coupled to a linear high polymer under conditions that would not affect the preformed triazine ring. Consequently, various a-halomethyltriazines (I) were prepared and their coupling reactions were studied using mercury as the coupling agent. Results and Discussion Precursors.-The synthesis of compound I required the preparation of the three nitriles, C1F2CCN, BrF2CCN, and IF&CN, and the anhydride, (BrCF&0)20. Chlorodifluoroacetonitrile was prepared from CCIF2CONHz as described previously.6 Bromodifluoroacetonitrile was synthesized by two different routes.
+
-
CFI=CF-CF=CF~. . Brz- +
1. KMnO4
CFzBrCF=CFCFzBr
2. H+-Et20
NHa
2CFzBrC02Et
+
H +-EtOH
2CFzBrCOOH -+ P~OS
+2CFZBrCONHz+2CFzBrCN
ultraviolet
C F ~ H Z3Brz ----+
-
(A)
PlO6
CFzBrCOOH
CFzBrC02R
(CF2BrCO)z0
1. NHa 2. PtOs
CFZBrCN
(1) (a) This work was performed under Contract AF 33(615)-1233, Elastomer and Coatings Branch, Air Force Base, Ohio 45433. (b) For convenience the prefix halo includes only chlorine, bromine, and iodine. (2) H. C, Brown, Abstracts of the 128th National Meeting of the American Chemical Society, Minneapolis. Minn., Sept 1955; the 134th National Meeting of the American Chemical Society, Chicago, Ill., Sept 1958; and the 147th National Meeting of the American Chemical Society, Philadelphia, Pa., April 1964.
Initially the bromodifluoroacetic acid used in this work was prepared according to route A. However, the cost of the starting material and the necessity of the permanganate oxidation step encouraged a search for a better route. Route B was readily adaptable to the production of large quantities of CF2BrCOOH or CFZBrCOzR, which served as precursors to (CF2BICO)~Oand CF2BrCN,respectively. Iododifluoroacetonitrile proved to be more difficult to prepare. CFzBrz
NaOH
peroxide
4- FzC=CHZ *CFzBrCHCFzBr 4 CFzBrCH=CFz
Ne1
+CFzICH=CFZ
CFzICOOEt
NHa ---t
1. KMnO4 2. EtOH
PtOa
CFzICONHz ---t CFzICN
Oxidation of an acetone solution of CF21CH=CF2, using neutral, aqueous KMn04 followed by esterification yielded the new compound, CF21C02Et. Decomposition of the ester during distillation, as indicated by the formation of large quantities of 1 2 , was thought to be one major cause of the low yield of product (20.6%). The ester was converted to CF21CONHz in good yield; treatment of this product with Pz06at temperatures barely sufficient to initiate dehydration afforded an 83% yield of pure nitrile, CF21CN. Triazine Syntheses.-The first perhalomethyl-striazine, tris(trichloromethyl)-1,3,5-triazine,was prepared by Dachlauer,6 via trimerization of CClaCN using anhydrous HC1. The first fluorine-containing perhaloalkyl-s-triazines were synthesized by McBee, Pierce, and Bolt7 by fluorination of the trimeric CClaCN with SbF3. The triazines used in this investigation were prepared by the method of Brown* because of its versatility. During this study the scope of this reaction waa extended to include halodifluoroacetonitriles and halodifluoroacetic anhydrides (Scheme I). Thus Ia was synthesized using CF2BrCN in step I, CF&N in step 11, and (CF&0)20 in step 111. The versatility of the reaction sequence is shown by the fact that I a was also synthesized using 2 equiv of CF3CN in step I (thus bypassing step 11) and (CFzBrC0)20 in step 111. Generally, triazines containing two or more identical groups were synthesized by by(3) D. R. Husted, U. S. Patent 2,676,985 (1954). (4) E. Dorfman, et d.,89th National Meeting of the Division of Rubber Chemistry of the American Chemical Society, San Francisco, Calif., spring 1966. (5) N. N. Yaroveneso, et al., Zh. Obahch. Khirn., 1’7, 2301 (1957). (6) Dachlauer, German Patent 699,493 (Oct 31, 1940). (7) E . T. McBee, 0. R. Pierce, and R. 0. Bolt, Ind. Eng. Chsm., SO, 391 (1947). (8) P. D . Schuman, Doctoral Thesis, University of Florida, Aug 1982.
VOL.32
GRINDAHL, BAJZER, AND PIERCE
604
TABLE I PREPARATION OF I Starting materials Compd
Step I
Procedure
Ia
B A Ib B IC A Id A Ie B If B Approximate data.
Step X I
Triazine distribution, glpc area %
Step I11
2CFaCN ... (CFZBrC0)zO CFZBrCN CFaCN (CFaC0)zO 2CF2BrCN ... (CFoC0)zO CFzClCN CFzClCN (CFaC0)zO CFaCN CFaCN (CFaC0)zO 2CFzBrCN ... (CFZBrC0)zO ... (CFaCO)zO 2CFzICN * 2,4,6-Tris(chlorodifluoromethy1)-1,3,5-triazine= 39%.
7' 14.5 51 74 28 31 15.8
Yield,
I a >90; Id, tracea Ia, 77.5; Ib, 8 . 1 ; Id, 14.4 Ib, 80.6; Ie, 19.4 IC,61b Id, 96 Ieo
If, -90
...
No reliable glpc data available.
TABLE I1 PHYSICAL CONSTANTS AND ANALYSES OF NEW COMPOUNDS BP, "C Compd
Is Ib Ie CFzICOzEt CFzICONHz CFJCN (CFzBrC0)20 CFzBrCN
%-
-C,
--F,
%-
%-
-N,
(mm)
n26D
d $64
Calcd
Found
Calcd
Found
Calcd
Found
130 82 (28) 112.5 (25) 144-145 Mp 99-99.5 46-47 121.8-124 3-5
1.3718 1.4200 1.4632 1.4373
1.804 2.015 2.16
20.83 17.71 15.40 19.22 10.81 11.84 14.48 15.40
21.2 18.13 15.52 19.25 11.7 11.9
43.91 32.68 24.37 15.20 17.20 18.72 22.90 24.37
45.0 33.0
12.15 10.33 8.98
11.40 10.12 8.90
.. ... ... .., ... ,
... ...
1.3912
...
SCHEME I NH -780 II CF,XC-NHZ
...
...
...
.
6.34 6.90
6.19 6.57
23.1 24.0
... 8.98
... .. .
14.9
..
,
, ,
--Halogen, Calcd
23.10 39.28 51.25 50.76 57.44 62.54 48.16 51.25
%Found
... 39.53 50.4 50.70 56.2
,.. ... ., .
mercury a t elevated temperatures. For example, 2bromodifluoromethyl-4,6-bis(trifluoromethyl)-l,3,5 - tri-783 -00 azine (Ia) underwent intermolecular debromination CF,XCN -k .NH, to yield 1,2-di [4,6-bis(trifluoromethyl)-1,3,5-triazinyl]n tetrafluoroethane (IIa, Scheme 111). Furthermore, CFzY the difunctional triazine, 2,4-bis(bromodifluoromethyl)NH NH, I 6-trifluoromethyl-l,3,5-triazine(Ib), underwent varying degrees of coupling, depending upon reaction conditions, to give linear polymeric chains ranging from a dimeric species to a chain of approximately 350 units Ia, X = Br; Y = F; Z = F (IIb). For example, a t a temperature of 160' for _X_ = -F : Y = F: Z = Br several hours I b yielded mainly a linear dimer, trimer, b, X = Br; Y = Br; Z = F C, X = C1; Y = C1; Z = F and tetramer which were isolated and characterized. d.X=F:Y=F:Z=F At higher temperatures or for a longer reaction period e,' X = B;; Y = B r ; Z5 = Br high polymers, with an average n 1 350, were formed. f, X = 1 ; Y = I; Z = F The molecular weight of the polymer obtained was calculated from end-group analysis data, assuming a passing step 11. For example, I e was synthesized using bromine-terminated polymer. The validity of this 2 equiv of CFzBrCN in step I and (CF2BrC0)z0 in assumption is supported by the following data. (1) step 111. Low polymer (n = 35-40), as well as pure dimer The product distributions and yields of these reactions are listed in Table I. New compounds are (n = 2), could be further coupled to high polymer, showing that coupled products are still difunctional. described in Table 11. Notice that the desired triazine (2) Elemental analyses of pure dimer, trimer, and is obtained as the major product in each case, but tetramer support a perfluoroalkylperfluoroalkylenevarying yields of other triazines are also obtained. For example, 2,4,6-tris(chlorodifluoromethyl)-l,3,5-tri- triazine structure in which this functionality is still the C-Br bond. (3) No macrocyclic compounds have been azine was not sought directly but obtained as a bydetected among the isolable, low molecular weight speproduct in the preparation of IC. The presence of cies. The coupled products are described in Table other triazines can be rationalized by the following 111. system of equilibria, using the preparation of I a as an The corresponding chloro compound, 2,4-bis(chloroexample. The intended route is shown with heavy difluoromethyl)-6-trifluoromethyl-l,3,5-triazine(IC),on arrows (Scheme 11). the other hand was relatively inert in the presence The presence of Ie found in the preparation of I b is of mercury. At 300' for 16 hr, ICgave a small amount more difficult to explain but could be due to a simple of a product which was not isolated, but rather detected trimerization of CF2BrCN. All the products of this by glpc and assumed to be IIc (n = 2, the balance of reaction could also be accounted for by assuming a the material). catalytic ring cleavage of I a and a random shuffling The completely fluorinated analog, 2,4,6-tris(triof two groups between three sites. Such a catalyst fluoromethyl)-l,3,6triaaine (Id), was completely inert was not sought. to mercury a t 250' for 16 hr. Indeed, it is this inertCoupling Studies.-It has been found that a-bromoness of the CF3 group that allows the formation of only perfluoromethyl-s-triazines display an unusually high dimer from Ia, and linear polymer from Ib. degree of reactivity toward coupling in the presence of
-
I
-
MARCH1967
605 TABLE 111 PREPARATION OF I1
-c, Product
%-
%-
-N,
Y
n
MP, O C
Cslcd
Found
Calcd
IIa
F
IIb IIb IIb IIb
Br Br Br Br Br Br
2 2 3 4 3 4 35-40 350
41.5 35.5-36 70-72 89-90 114-117 135-138 >350
27.08 22.04 23.99 25.11 23.99-25.11 28.64-28.70 29.11
27.3 22.3 24.8 26.3 24.4
15.79 12.85 13.99 14.64 13.99-14.64 16.70-16.74 16.97
(dimer) (trimer) (tetramer) (prepolymer) IIb (low polymer) I I b (high polymer)
,
..
27.7
-
Br, %
Found
Cslcd
15.1 12.1 13.3 14.1
... 24.44 17.74 13.92 17.74-13.92 1.81-1.59 0.18
...
... 16.4
Found
... ... ... ... 16.2,15.6 1.56-1.64
