identity with bagasse native lignin is well founded. This identity rnay be further recognized in thrir infrared and ultraviolet absorption spectra4 l n a forthcoming communication this conclusion will be further supported by means of oxidation studies with nitrobenzene and alkali and also by identiiying their lignosulfonic acids. Acknowledgments.-The bagasse used in these experiments was obtained through the courtesy
\CoVTRrnVTIOS FROM
of the Godchaux Sugars, Inc., New Orleans, La. The inold cultures used in this investigation were obtained through the courtesy of Dr. W. J. Robbins of the Kew York Botanical Garden. The analyses reported in this paper were carried out by Mr. A. -4. Sirotenko of this Department. This work was carried out under the auspices of the Office of Naval Research. SET?' Y O R K , F.Y.
'I'IIE nEPARTMES1' OF CfIERIISTRY A Y D THE r)EFEXSE RESEARClf I,ABORATORY, T E As
Allylic Chlorides.
x 1
THEI!NIVERSITP
OF
XVIII. Preparation and Properties of 1,1,3-Trichloro-2-fluoro-lpropene and 1,1,2,3-Tetrachloro-1-propene' BY LEWISF.HATCH AND DAVID W. MCDONALD? RECEIVED DECEMBER 22, 1951
The following compounds have been prepared and characterized for the first time : 3-bromo-l,l-dichloro-2-fluoro-lpropene, 3,3-dichloro-2-fluoro-~-~~ro~~e1i-l-ol, 1,1,3-trichloro-2-fluoro-l-propene, 2,8,X-trichloro-2-propen-l-ol and 1,1,2,3zind 1, I ,~,3-trtrachloro-l-prope11e with potassitim tetrachloro-I-propene. The reactions of 1,1,3-trichloro-~-fl~toro-l-properle iodide and with sodium ethoxide hnvc hwii studied
The study of the influence of various groups and pene was related to 1,1-dichloro-2-fluoro-~ -propene atoms on the reactivity of the allylic chlorine atom by replacement of the allylic chlorine atom by a of substituted allyl chloride has been extended to hydrogen atom using lithium aluminum hydride.6 include lI1,3-trichloro-2-fluoro-l-propene and 1,1,- The structure of 1,1,2,3-trichloro-l-propenewas 2,3-tetrachloro-l-propene. Both of these cum- also confirmed in the same manner by its conver' I sion to the known 1,1,2-trichloro-l-propene.7 pounds are of the type CC12=C-CH,CI, a type The relative reactivities of 1,1,3-trichloro-2which shows a marked difference in its reaction fluoro-1-propene and 1,1,2,3-tetrachloro-l-propene with potassium iodide in acetone from the similar with sodium ethoxide in ethanol (Table I) show the tvpe CR.-C- --CI I,CI. same relationship between the electron-attracting ' 1 The 1,1,3-trichloro-2-fluoro1-propene was syn- ability of the substituent on the number two carbon thesized from l,l-dichloro-2-fluoro-l-propeneby atom and reactivity as do those compounds having the use of N-bromosuccinimide followed by hydrol- two hydrogen atoms on the number one carbon atom.* I n both series the replacement of the hyysis of the S-bromo-l,l-dichloro-2-fluoro-l-propene to 3,3-dichloro-2-fluoro-2-propen-l-ol and conver- drogen atom on the number two carbon atom by an sion of this allylic alcohol to the desired allylic electron attracting atom (Br, CI or F) causes a dechloride in a manner similar to that previously used crease in reactivity. This similarity does not to prepare the 1,3-dichloro-2-fluoropropenes from TABLE I the 1-chloro-Zfluoro-1-propenes.'The 1,1,2,3-tetRELATIVE REACTIVITY O F 1,1,3-TRICHLORO-2-FLUORO-1rachloro-1-propene was obtained by the dehydroPROPENE AND 1,1,2,3-TETRACHLOR0-1-PROPENEWITH S O chlorination of 1,1,2,2,3-pentachloropropane. DIUM E T H O X I D E I N ETHANOL AT 50" The pentachloropropane was prepared by the 1,1,3-Trichloro-2-fluoro-l-propene low temperature addition of chlorine to 1 ,2,3-trichl~ropropene.~Apparently no substitution ocTime, hr. 6.50 8.50 10.5 12.5 22.0 curred which conforms with the generalizations of Reacted, 7 5 8 , 6 63.3 67.4 70.7 81.9 Taftl on noti-activated, low temperature c 1 i l o r i n : t k , hr.-I mole-'I. 4 . 3 7 3.88 3.87 3.81 3.83 tion reactions. The pentachloride obtained by the Av. k 3 .95fO. 16 addition of chlorine t o l,Z,R-trichloropropene is Rrlutive reactivity' 3.3 considered to be I , 1,2,2,3-pentachlori~propnne,alI , 1,2,3-Tetrachloro-l-propene though the physical constants of this compound do Time, hr. 1.00 1.50 2.00 3.00 4.00 not agree very closely with those reported by StevReacted, % 30.1 43.5 50.7 60.7 67.9 ens,j which disagreement, however, is prohxblv due k, hr.-'rriole-l I. 1 1 . 3 10.2 10.3 10.4 10.6 i n part to the higher purity of our sample. Av. k 10.6f0.3 The structure of 1,1,3-trichloro-"-fluoro-l-pro(1) For number XVII of this series see I,. F. l r a t c h a n d D. W. McDonald. THISJ O U R N A L , 74, 2911 (19.52). (2) Research Corporation Fellow 1D4O-~IOJO,~ f o i i s a n t o Fellow, 1 0 30 - 19 5 I . (3) L. F. IIatch. J. j . U'Amico and E. V. Riihnke, Tiirs J O I I I I N \ L , 74, 123 (1Y.52). (4) R . W. T a f t , i b i d , T O , 33G4 (1948). ( 5 ) P. C,. S t e v e n s , ibid., 68, 620 (1!14Ci)
Relative reactivitya 9.0 Allyl chloride as 1.00 with k = 1.18.
(6) L. 1'. H a t c h and R. H. Perry, ibid., 71, 3262 (1949). (7) G . Bersche and R. Fittig, A n n . , 133, 117 (1865); W. Szenic and R.Taggesell, Ber., 28, 2GG8 (1885). CSj I. P. 1T:itc.h i l ~ i < lTI, 1'. Alexander, TJIISJOVRNAI., 71, 1037 (1949)
July 5, 1952 4000 2500
2 90 c= 'io 50 D30 10
-
3329
1,1,3-TRICHLORO-2-FLUOROAND 1,1,2,3-TETRACHLORO-1-PROPENE Wave number (cm-1). 1400 1000
800
700
4000 2500
Wave number (cm-I). 1400 1000
800
700
p\\/J
I- , - $
4
1'
\J"d\Jl ,
/\*
6 8 10 12 14 Wave length in microns. 1,1,3-trichloro-2-fluoro-l-propene;F, 3Fig. 1.-E, bromo-l,l-dichloro-2-fluoro-l-propene;G, 1,1,2,3-tetrachloro-1-propene; H, 1,1,2,2,3-pentachloropropane. 2
4
Figure 1 gives the infrared spectra of the compounds prepared in this study. These spectra show no characteristics which are not in agreement with the assigned structures. Acknowledgment.-This investigation was supported in part by Task 2 funds of the Defense Research Laboratory, The University of Texas, operating under Contract NOrd-9195, Bureau of Ordnance, Department of the Navy. The authors are also grateful for the financial assistance given for this work by the Rescarch Corporatioil and the AIonsanto Chemical Co. Experimental 3-Bromo-1,l-dichloro-2-fluoro- 1 -propene.-I , 1- Ilichloro-
2-fluoro-1-propene (Halogen Chemicals, Itic., Columbia, South Carolina) was dried and distilled through an 18-inch glass-helix packed column to give a product with the following constants: b.p. 77.7" (715 mm.); n z s ~1.4196, l t S o ~ 1.4168; dZ6(1.3026, d304 1.2953 (lit.ll b . p 77'; n Z o1.4211). ~ A mixture of 1.42 moles of 1,I-dichloro-2-fluoro-l-propene, 1.00 mole of PIT-bromosuccinimide,0.10 mole of benzoyl peroxide and 550 ml. of carbon tetrachloride was refluxed for 3.5 hours.'* The product was worked up in the ( 1 1 ) Data Sheet, IIalogen Chemicals, Inc., Columbia, South Carolina. (12) K. Ziegler, A . Spath, E. Schaff, W. Shumann and E. Winklerman, A n n . , 661, 80 (1942).
:3:W
LEWIS17. H A T ~.IND H Davru U'. AICDONALU
Vol. 74
usual manner and distilled through the 18-inch column to
2,3,3-Trichloro-2-propen-l-ol.-l,1,2,3-Tetrachloro-1give a 59% yield of 3-bromo-l,l-dichloro-2-fluoro-l-propene propene (0.25 mole) was stirred for 18 hours at 70" with based on the S-bromosuccinirnide: b.p. 52" f20 mm.); I O U % molar excess of sodium carbonate in a 10% solution. ?L"D 1.5130, PZ'OD 1.5103; dZ541.8069, d304 1.7983. The reaction mixture was worked up in the usual manner 3,3-Dichloro-2-fluoro-2-propen-l-ol.--The3-bromo-1,l- and distillation through the 18-inch column gave a 51% tlichloro-2-fluoro-1-propene (0.53 mole 1 was hydrolyzed to yield of 2,3,3-trichloro-2-propen-l-o1:b.p. 199' (745 mm.), 3,3-dichloro-2-fluoro-2-propen-I-olby the use of a 10% 88-89" (16-17 rnm.\; w25n 1.5193, na% 1.5178; d*54 1.5553, solution of sodium carbonate (1.00rnolesi a t 70" for five d304 1.5496. hours. The product was worked up in the usual manner L4nui.13 Calcd.: Cl, 66.3. Found: CI, 66.1, 66.3. :inti distilled through the 18-inch coluriiii. A 74% yield 1,1,2-Trichloro-1-propene.-1 ,1,2,3-Tetrachloro-l-pro\vas obtained: b.p. 61 O (10 r n m . ) ; n 2 5 1.3ii70, ~ 7 1 3 O ~1.4650; pene (0.13 mole) was treated with 0.038 mole of lithium i 1 2 5 4 1.5032, d3'4 l.497U. aluminum hydride in tetrahydrofuran for ten hours a t reflux :lna1.13 Calcd.: C1, 48.9. Found: Cl, -k7,8, temperature. The reaction mixture was worked up in the 1,1,3-Trichloro-2-fluoro-l-propene.-The1 , l ,a-trichloro- usual manner and distilled through the 18-inch column. A 2-fluoro-I-propene was prepared by the action of phosphorus 56% yield of, 1,1,2-trichloro-l-propenewas obtained with a trichloride (0.14 mole) on 3,3-dichloro-2-fluoro-2-propen-l-ol 70% conversion: b.p. 114-115' (746 mm.); n2% 1.4798. (4.35 mole) in pyridine (0.08 A 50% yield was nZ0D 1.4780; d2929 1.341; lit.i b.p. 116", 116-117'; d " , , obtained: b.p. 129" (747 mm.), 42.5' (35 mm.); nzoD 1.387. 1.4710, nZ51)1.4689, dS, 1.5077, dS4 1.4999. Infrared Spectra.-The infrared spectra data were obtained through the courtesy of R. E . Kitson and the ChemiAni11.~3 Calcd.: C1, 65.1. Found: Ci, 64.5, 64.7. l,l-Dichloro-2-fluoro-l-propene.-Thestructure of the cal Division, Polychemicals Department, E. I. du Pont dc 1,1,3-trichloro-2-fluoro-l-propene (0.07 mole) was con- Xemours and Company. The spectra were made in the iirmed by the replacement of the allylic chlorine atom by hy- liquid phase using a Perkin-Elmer Model 21 double beam tirogen using lithium aluminum hydride (0.024 mole) in spectrometer. Sodium chloride optics were used with a cell diethyl ether.'j A 37% conversion with a 51% yield was thickness of 0.035 mm. for 1,l-dichloro-2-fluoro-l-propenc, 3-bromo-l , 1-dichloro-2-fluoro-1-propeneand 3,3-dichloro-2obtained of 1 , I -dictiloro-3-fluoro-l-propcne (b.p. 76.5-78"; fluoro-2-propen-l-ol, 0.037 mm. for 1,1,3-trichlor0-2-fluoron 3 0 ~1.4157). 1-propene and 0.040 mm. for the other compounds. 1,1,2,2,3-Pentachloropropane.--The 1,1,2,2,3-pentaReaction with Potassium Iodide in Acetone at 20".---The chloropropane was prepared by the addition of chlorine t o usual procedure was usedl6; however, the data obtained 1,2,3-trichloropropene3( 1 . S I moles) a t 10' over a period of mere not arneuable t o calculation on the basis of a secondeight hours iii the presence of light supplied by three 200- order reaction. The 1,1,3-trichioro-2-fluoro-l-propene reivatt light bulbs placed adjacent to the reaction flask. Ilis- acted to the extent of 53% in 0.25 hours, 2 . 4 % in 1.50 tillation of the reaction mixture through a three-foot glass- hours and 72.8% in 3.00 hours, while 1,1,2,3-tetrachloro-Ihelix packed colu~niigave a 74% yield of 1,1,2,2,3-penta- propene reacted t o the extent of 53.5% in 0.25 hours, 54% chloroproparie: b.ji. 198" (742 nim I , 73-79" (16 111m.); in 1.00 hours and 61.8% in 2.00 hours. n2% 1.5080, ? L ~ D1,505.3; d 2 j , l.fj199, ddu41.6130; lit.: Reaction with Sodium Ethoxide in Ethanol at 50°.-Thc b . p . 191- 191.5' ( i s 5 iiini.); n ? j 1.5098; ~ d ? j 41.63%. procedure used was the same as that previously describeds .Inul.'3 Calcci.: CI, Su.1cj. Found: Cl, 80.00, 8O,O(j. and the data were calculated using the rate expression for 1,1,2,3-Tetrachloro-l-propene. ---l,i,2,2,3-Peiitachloro- a second order reaction. The sodium ethoxide solutioii propane (1.09 moles) and ethanol (184 g . ) were treated in 3 was 0.05003 Jf for the reaction with 1,1,3-trichloro-2stirred one-liter flask with 1.09 moles of potassium hpdros- fluoro-1-propene (0.05006 M ) and 0.05005 .llfor the reaction with 1,1,2,3-tetrachloro-l -propene (0.0SOt50 31;. ide added portionwise over a period of six hours. After A plot of log b(u - z)/a(b- x) os. time gave a straight linc one hour of reflusing and two hours at room temperature, between 46 and 82% the reaction mixture was worked up in the usual itiaiitier and for 1 , l ,~~-tricl~loro-2-fluoro-l-propene distilled through the 18-inch column t o give a 64% yield reacted arid between 3,5 and 68% reacted for the 1,1,2,3tetrachloro-1-propene. l,l-Dichloro-2-fluoro-l-propenercof 1,1,2,3-tetrachloro-l -propene : b .p. 182' (743 inin. ), b.p. 59' (17 min.1; nZ5n1.5174, n3O~1.3150; d2j, 1.5488, acted to the extent of 10% in 120 hours ryith sodium ethoxide S o correction was made for this csteiit i i i ethanol at 50'. (I", 1.5424. of reaction of the \-illy1 1i:iliilc.; i i i cxlculatirig thc rcactioii .lnu1.'3 Calctl.: C1, 18.8. 1;ound: C1, 7 S . l . i - ~ t of e :illylic. cliloi-iiie:itoiii. ~
(1:lj E. Chablap, A n t i . c h i m . , 1, 510 ( 1 9 l r i . (141 A. Juvala, Bcr., 63B, 1983 (1930); 1,. I;. 1l:rtch an11 ,-. S S r s h i t t , THISJ O U R K A L , 72, '727 (1950) (1;) 1. F. Hatch aiid R 11 I'erry, i i i l r f 7 1 , 3262 \ I
, I C , ) 1. 1.' l r C ~ t c l i1.. , li
' I!)i8
(;01
