94%
Vol. 67
ARAMMOORADIAN AND J. B. CLOKE [CONTRIBUTION FROM
THE
WALKER LABORATORY OF THE RENSSELAER POLYTECHNIC INSTITUTE 1
The Synthesis of 3-Chloro-2-chloromethyl-1-propenefrom Pentaerythritol BY ARAMMOO RADIAN^ A N D J. B. CLOKE
The present work on 3-chloro-2-chloromethyl- hydrolysis in the presence of calcium carboilate 1-propene (I), H~C=C(CHL!l)z, was undertaken to give the glycol, (HO--CH&C=CHZ (VI) ;. for in connection with a study of certain chlorinated the unsymmetrical compound (111), as shown by ethylenic hydrocarbons and nitriles to be re- Pogor~helski~is saponified by 10% potassium ported in a later paper. KleinfellerZ first an- carbonate solution to give the 8-chloro-alcohol, nounced the preparation of a mixture of (I) and ClCH==C(CH*)CHsOH, in which the halogen 1,3-dichloro-2-chloromethyl1-propene (11) in attached to the doubly linked carbon is not re70% yield by the action of sodium amalgam on 5 placed by hydroxyl. Furthermore, (I) has a g. lots of 1~3-dichloro-2-nitro-2-chloromethylhigher melting point (-15 to -13') than (111) propane, OtN-C(CHC1)S. Although Kleinfdler (below -65),* which is also in harmony with the reported the separation of (I) and (11)in the pure symmetrical structure. Measurements of the state, he failed to state the yield of each. For ob- dipole moment of (I)8 were inconclusive on vious reasons, his method does not recommend account of certain experimental difficulties. The itself for the preparation of the compound in question of the rearrangement of (I) into (111) significant quantities. has not yet been investigated. More recently, a mixture of (I) and the isoThe tris-(chloromethy1)-acetic acid (IV) or meric 1,3-dichloro-2-methyl-l-propene(111) C1- sym-trichloropivalic acid, presumably a new comCH==C(CH~)CHZCI,which may exist in cis and pound, was obtained by the nitric acid oxidation trans forms, was obtained by the pyrolysis of of pentaerythrityl trichlorohydrin (VII), which, 1,2,3-trichloro-2-methylpropane, a and also by the in turn, was prepared from pentaerythritol (VIII) chlorination of isobutene and methallyl chlo- by the use of thionyl chloride and pyridine ride.416eBHowever, no account has yet appeared (H0CHn)rC+(CICH2)cCCHaOH+(ClCHZ),CCOnH on the separation of this mixture. It would WII) (VI11 (IV appear that this might be accomplished through The reaction of pentaerythritol with thionyl the hydroxy derivatives. Since the foregoing methods are unsatisfactory chloride had been studied previously by other for the synthesis of (I) in quantity and in the pure workers. In the first work, Orthner'O o6tained state, several alternative methods were investi- only a disulfite derivative which Bougault" had gated. A satisfactory preparation involves the prepared by the action of sulfur monochloride on decomposition of tris-(chloromethy1)-acetic acid (VIII). More recently Govaert and Hansens" (1,3 - dichloro - 2 - chloromethyl - 2 - propane- treated pentaerythritol with both thionyl chloride carboxylic acid) (IV) in the presence of hot and thionyl bromide in the presence and absence quinoline, whereby 7 5 4 5 % yields of (I) are ob- of both pyridine and diethylaniline in the expecta tained. It may be assumed that the first stage tion of obtaining the mono-, di- or trihalogen in the reaction is the decarboxylation of (IV) to derivatives, but they reported a quantitative give 1,3-dichloro~2-chloromethylpropane (V), yield of the disulfite only and no halogenated whch then undergoes a dehydrohalogenation to products. The reference to this work was found, perhaps fortunately, only after we had obtained give (1) the tetra-, tri-,di- and possibly the mono-chlorine (ClCHz),CC02H +(CICH9)nCH +(ClCH,)sC=CHz substitution products of VI11 by the same reaction (IV)
(V)
(1)
Our synthesis of (I), like that of Kleinfeller,2 points to the symmetrical structure (I) rather than (111). That this is the case, a t least for the bulk of the compound, is borne out by its relatively sharp and higher boiling point and by its (1) This paper has been abstracted from the second part of a thesis presented by Aram Mooradian to the Rensselaer Polytechnic Institute in June, 1941, in partial fuI6llment of the requirements for the degree of Doctor of Philosophy. (la) Present address Winthrop Chemical Company, Rensselaer,
N. Y. (2) Kleinfeller, Bcr., 648,1590 (1929). (3) Rogers and Nelson, Tars JOURNAL, 68, 1027 (1936). (4) Burgin, Engs, Oroll and Hearne, J. Znd Eng. Chcm., 31, 1413 (1939). (5) Burgin, Hearne, Rust, %bid.,33, 385 (19411, Suter and Bordwell, THISJOURNAL, 66, 507 (1943). (6) Dyakonov, J . Gcn. Chcm.. U.S S R , 10, 402 (1940).
C(CH20H)c +CICHzC(CH20H)r + (VIII) (IX)
(CICHz)2C(CHzOH)z +(CICH2)sCCHzOH +
(X,
(VII)
C(CH9CI)4 (XI)
As had been reported by the earlier workers, we obtained the disulfite compound when the reac(7) Pogorshelski,*J. Russ. Phys.-Ckcm. Soc., 36, 1129-1184 (1904) : Chcm. Zcnfr., 76, 668 (1905). (8) Mooradian, "Thesis," R.P.I., 1941, Mooradian and Cloke, communication in preparation for THISJOURNAL. (9) De Lalln, "Thesis," Rensselaer Polytechnic Institute, 1941. with Dr. 0. M. Arnold. (10) Orthner, Bm., 61B,116 (1928). (11) Bougault, C o m p f . r e n d . , U S , 188 (1896). (12) Govaert and Hansens, .Veluurw. Tijdschr., 21, 215 (1940); Chcm. Abs. 34, 3680 (1940).
June, 1946
%cHLORO-2-CHLOROMET€iYL1-PROPP,NE FROM PENTAERYTHRLTOL
943
with joint, provided with a long Allihn condenser also with T ground joint. The apparatus was set up in an efficient hood and 300 cc. of concentrated nitric acid was poured into the flask, after which the mixture was heated cautiously. At fist the chlorohydrin dissolved and then two layers appeared. About this time the beginning of a reaction became apparent, whereupon the flask was rapidly lowered into a waiting bath of cold water and the operator withdrew. When the first violent reaction was Experimental Part Over and the evolution of nitrogen oxides had practically Pentaerythrityl Trichlorohydrin (VU).-To a mechani- ceased, the flask washeated carefully until no more brown cally stirred, externally ice-cooled slurry of 408 g. (3moles) fumes were evolved. At the end of this period, a clear of pentaerythritol (Niacet Co.) and 711 g. (9 moles) of almost colorless solution resulted. The dilution of this pyridine, (Barrett) contained in a flask, a weight of 1071 g. wit'h water led to the precipitation of a quantitative yield (9 moles) of thionyl chloride was added drop by drop a t of crude acid of m. p. 108-110'. The crystallization of such a rate that the white mist appearing in the flask did this from petroleum ether gave a product of m. p. 112.8not rise up into the condenser. After about one-thud of 113" (cor.). the thionyl chloride had been added a t this rate, the Calcd. for CbHlOzCb: C1, 51.78. Found: remainder b a s dropped in quite rapidly. When the C1,Anal. 51.87,52.10. addition was complete, the whole was heated under a The acid also may be crystallized from benzene, chlorod u x condenser until no more sulfur dioxide was evolved. After cooling, an equal volume of water was added, form and carbon tetiachloride. Amide of (IV).-The acid is readily converted to the whereby, on standing, a water layer and water-insoluble layer apppred. The water layer was decanted and amide by the use of thionyl chloride and aqua ammonia. extracted three times with benzene. It was then extracted After it was recrystallized from water, the amide melted a t 121-122% (cor.). continuously with ether in a special apparatus.14 The combined benzene extract and water insoluble layer Anal. Calcd. for CSHRONCI~:N, 6.85. Found: N, was fractionated under diminished pressure and gave 7.00,7.03. 50-80 g. of crude pentaerythrityl chloride b. p. 95-110' 3-Chloro-Z-( chloromethyl) -1-propene (I).-Equimolar a t 12 mm., 305-341 g. (5349%) of pentaerythrityl tri- quantities of quinoline and crude tris-(chloromethyl) -acetic chlorohydrin, b. p. 127.5-129' at 12 mm., m. p. 65.5' acid were mixed and heated under a reflux condenser until (cor.),l6 and 20 g. of pentaerythrityl dichlorohydrin b. p. a reaction started. Half mole runs were found to be 150-160' at 12 mm. The ether extract gave an addi- preferable. A t this point heat was removed and the retional 24 g. (4%) of pentaerythrityl trichlorohydrin and action allowed to proceed of its own accord. When the 42 g. of dichlorohydrin, b. p. 150-160' at 12 mm. reaction subsided, a fractionating column was attached Anal. Calcd. for CsHoOCL: C1, 55.55. Found: C1, to the flask and all material distilling below 135' was distilled out of the reaction mixture as it was formed. 55.71,55.80. Pentaerythrityl Dichlorohydrin (X).-The procedure The dried redistilled dichloro-isobutylene boiled quite melted from -15 t o -13', used was identical with that employed in making the tri- sharply a t 13&138.3', chlorohydrin (VII) with the exception that the molar ratio and was obtained,in a yield of 75-85%; d204 1.1782; of pyridine and thionyl chloride to pentaerythritol was nZ0D 1.4754; M R D calcd., 29.94; M R D obsd., 29.90. two to one rather than three to one. In this case, most of Anal. Calcd. for CIH&IZ: C1, 56.73. Found: C1, the desired material was found in the ether solution ob- 56.73,56.86. tained by continuous extraction. The mixed ether extract, The isomeric compound (111)8 boils at 131-132.5' and benzene extract, and water insoluble layer was distilled is liquid a t -85'. giving from a One mole run 70 g. of pentaerythrityl di3-Hydroxy-Z-( h y d r o m e t h y l )-1-propene (VI) .-A chlorohydrin (40%) b. p. 158.5-160' a t 12 mm., m. p. weight of 28.5'g. (0.23mole) of 3-chloro-2-(chlormethyl)83' (cor.),16 28 g. of pentaerythrityl trichlorohydrin and 1-propene was mixed with 125 cc. of water and 46 g. a small amount.of material of b. p. 183-188' at 16 mm., (0.46mole) of calcium carbonate and heated under reflux probably pentaerythrityl monochlorohydrin. for seventy-two hours. The solid in the reaction mixture Anal. Calkd. for CsHleOzClp: C1, 40.99. Found: was collected on a filter and the water solution distilled C1,41.10,41.12. giving 7.3g. of material (36%) of b. p. 125-126' a t 18mm.; Pentaerythrityl Tetrachloride, Tetrakis-(chloromethy1)- d20, 1.0791;n2% 1.4758; M R D calcd., 23.25;MRD obsd., methane (=).-The procedure used for (XI) was the 23.02. same as for (VII) and (X) with the exception that a molar Anal. Calcd. for C4H80z: C, 54.53;H, 9.15. Found: ratio of four to one was used in this case. At the end of C, 54.80; H, 9.00. the period of heating, the dilution of the reaction mixture Bromine Absorptive Capacity of 3-Chloro-Z-(chlorowith water completely precipitated the product. The methyl)-1-propene.-Using McIlhiney's method as outwater layer was decanted and discarded and the insoluble lined in Meyer,l* a quantitative study of the bromine portion distilled. The product from a one mole run absorptive capacity of 3-chloro-2-(chloromethyl)-l-proamounted t o 160 g. (76%) of pentaerythrityl tetrachloro- pene was carried out. A t the end of eighteen hours in hydrin, b. p. 100' a t 12 mm., m. p. 97' (cor.). carbon tetrachloride solution in the dark, no appreciable Anal. Calcd. for CsHsCl,: C1, 67.57. Found: C1, addition (2.9%) or substitution was observed. 67.73,67.80. Tris-(chloromethy1)-acetic Acid (IV) .-A weight of summary 0.75 mole (143.6 g.)" of pentaerythrityl trichlorohydrin was transferred to a three-liter, round-bottomed flask , , 1. The action of thionyl chloride on penta-
tion was carried out in the absence of organic base. Previous to our work, the only successful method for the preparation of (VII) involved the action of hydrochloric acid on (YIII), whereby small yields of (VII) and the three other possible products (IX), (X) and (XI) were obtained.la
(13) Fecht. Ber., 40,3888 (1907). (14) A two-liter extraction apparatus, e. E., Ace No. 6835; Scientific Glass Apparatus Co., No. J-1628B; Ashley and Murray, I n d . Eng. Chem., A n d . Ed., 10,367 (1938). (15) Fecht, Zoc. L i t . , reported a m. p. of 80' and b. p. of, 136' at 12 mm. (16) Fecht reported a m. p. of 06' and b. p. of 160' et 12 mm. (17) On account of the violence of the reaction, the use of a larger quantity is not recommended. Half-molar amounts are pcefemble.
ejthritol in pyridine solution leads to the successive replacement of the four hydroxyl groups. However, only the di, tri and tetra chloro derivatives have been isolated. 2. The oxidation of pentaerythrityl trichlorohydrin with nitric acid gave a quantitative yield (18) H.Meyu, "Lehrbuch der organirch-chemischen Methodik,"
Vol. I, p. 1126.
Vol. 67
ERICHBAL'KANI) HERMANN 0. I,. FISCHER
944
of tris- (chloromethyl)-acetic acid, presumably
new compound. 3. The action of hot quinoline on tris-(chloromethyl)-acetic acid gave a good yield of 3-chloro-
8- (chloromethyl) - 1-propene, whose structure is supported by its saponification to give the corresponding glycol. TROY, NEW YORK
RECEIVED MARCH13, 1945
[CONTRIBUTIONFROM THE DEPARTMENT OF CHEMISTRY, BAXTLYG INSTITUTE, UNIVERSITY OF T o R o m o ]
Conversion of D( +)-Acetone Glycerol into its Enantiomorph BY ERICHBAERAND HERMANN 0. L. FISCHER In principle any optically active substance whose asymmetry is due to substitution in one of two otherwise identical groups can be converted into its antipode by interchanging the position of the substituent (Scheme A). E. Fischer and Brauns' succeeded in exchanging the position of the hydroxyl and amide group of the dextro-rotatory isopropylmalonamidic acid and obtained the levo-rotatory isomer with practically no loss in optical activity. This successful conversion is still regarded as an excellent experimental confirmation of the spatial concept of the asymmetric carbon atom as postulated by van't Hoff and Le Bel. In 193T the authors reported in a preliminary note, without giving experimental details,2 the conversion of D(+)-acetone glycerol into L( -)acetone glycerol. The levo-rotatory isomer was obtained by transposing the acetone group. The directing of this group into its new position and the maintenance of the optical activity of the molecule during the six steps of the conversion were accomplished by a series of asymmetric substitutions of the glycerol molecule as shown in Scheme B which also illustrates the steric relationships of the intermediary compounds. SCHEME A
R
D( +)-Acetone glycerol (I) was nitrobenzoylated in pyridine and the resulting nitrobenzoate (11) was deacetonated in 0.5 N hydrochloric acid at 73 to SOo. The tritylation of L-(P-nitrobenzoyl) glycerol (HI) in pyridine gave L-(p-nitrobenzoyl)-glycerol-trityl ether (IV). Saponification of IV with sodium hydroxide iq ethanol yielded D-glycerol-trityl ether (V) which on acetonation with zinc chloride in acetone formed L(-)-acetone glycerol-trityl ether (VI).a Catalytic removal of the trityl group in compound VI with hydrogen in the presence of palladium on charcoal resulted in the formation of tone glycerol (VII) which was identical with L( - )-acetone glycerol prepared from L-mannitol.' Because of the numerous reactions involved, the L( -)-acetone glycerol was obtained in a yield of 6 6 % only. Its optical activity was 12.5% less than that of D(+)-acetone glycerol. This small loss in optical activity must have occurred during detritylation, since the rotation of L( --)-acetone glycerol-trityl ether prepared by tritylation of L( -)-acetone glycerol is the same as that of L( -)acetone glycerol-trityl ether obtained by conversion. Early in our work dealing with the synthesis of optically active gly~erides,~ the need for L(-)acetone glycerol as a starting material for the synthesis of the D-series of a-mono-glycerides a r a e and its preparation froni D( +)-acetone glyc-
ace-
(1) D(+)-Acetone glycerol [ a ]+14.0" ~
HIC- .--0 -C(C aH 4 1
(IV)
HIC---.C) -C(CeH*),, i \ I)
i\1
--__ (I) E. Piocher and F . Brauns, E m . , 47, 3181 (1914); cf. Henry Gilman, "Organic Chemistry." second edition, John Wiley and Sons, Inc.. New York, N. Y.,1943, Vol. I, p. 227. (2) Natvrwirrcnschuften. 96, 588 (1937)
H~--OH (VII) L( --)-Aceto11r g 1y ce1'o1 [aID - 1 2 . 2 O
(3) Another method of preparation of thiscompound by tritylation )-acetone glycerol is also described in the experimental part. (4) E. Baer and H. 0. L. Fischer, THIS JOURNAL, 61, 761 (1939). (5) E. Baer and H. 0. L. Fischer. J . B i d . Chem., 148,475 (1939)
of L(
-
