The Grignard Reagent in Hvdrocarbon Synthesis J
J
CECIL E. BOORD, ALBERT L. HENNE, KENNETH W. GREENLEE, WARREN L. PERILSTETN, AND JOHN M. DERFER The Ohio State University, Columbus, Ohio T h e Grignard reaction has been adapted to the preparation of a large number of hydrocarbons on enlarged laboratory scale. Special metal reactors were designed for this purpose. Generalized production and purification procedures are presented. Specific data, including methods of preparation, yields, physical properties, and literature references are given in tabular form for about 80 hydrocarbons.
T
H E American Petroleum Institute Research Project 45,' formerly known as the American Petroleum Institute Hydrocarbon Research Project, completed its ninth year of operation on June 30, 1947. A total of 163 individual hydrocarbons has been synthesized and purified in quantities from 0.5 pint to 5 gallons. Of this number, about half were prepared by schemes involving the Grignard reaction in one or more steps; some of these were prepared by two or three alternative methods. Eight distinct types of Grignard reactions played a part in this work. T h e synthetic procedures used were based on 12 years previous experience in the synthesis of olefins, diolefins, and phenyl olefins and their hydrogenation t o the corresponding saturated derivatives (3, 26, 79-81, 85, 86). The present paper summarizes the Project's activities in this field and gives an over-all view of the Grignard reaction as a preparative method for the production of pure hydrocarbons. METHOD
The methods best adapted to the synthesis of olefins, diolefins, and phenyl olefins in quantity often involve the use of the Grignard reaction. An aldehyde, ketone, or ester is reacted with a Grignard reagent to form a carbinol. The carbinol is dehydrated to produce an olefin or a mixture of olefins which usually can be separated by efficient fractionation. An alternative method involves the condensation of an allylic halide with Grignard reagent to form the olefin directly. Unsaturated hydrocarbons of given carbon skeleton are more numerous and more readily synthesized than saturated hydrocarbons. In the usual case a saturated hydrocarbon is produced most readily by hydrogenation of an unsaturated hydrocarbon with the desired arrangement of carbon atoms. This principle is a general one and is applicable t o both cyclic and noncyclic types. Mono-olefins Diolefins Acetylenes Cyclo-olefins Cyclodiolefins Aromatics
\+ \1 +
J
Hydrogen
Hydrogen
-+- Paraffins
REACTORS
The use of the Grignard reaction to produce materials in quantity calls for equipment larger than is normally used in the laboratory. Reactors were designed especially for this purpose. Four of these were constructed of steel and had a capacity of 15 gallons each. Two smaller reactors of 2- and 5-gallon capacity were constructed of steel but were copper lined; these were used largely in experimental runs. The performance of both types was highly satisfactory. These metal reactors are used for each of three standard operations involved: preparation of the Grignard reagent; the condensation reaction; and the quenching of the reaction product. The larger reactors will handle charges of 50,75,and 100 gram moles, depending on the nature of the charging material and the type of operation involved. The detailed design of the 15-gallon reactor is shown in Figure 1. The steel reaction vessel, A, is surrounded by a sheet metal jacket, D, making it possible t o cool the reactor by t a p or ice water, or t o heat it by hot water or steam. The tempering medium entering a t I circulates below and around the reactor, from bottom to top, and exits a t the top of the jacket. The arrangement makes i t possible to operate the reactor from below 10 O to about 100 C. The stirrer is shown by E: construction is sturdy and i t is driven b a motor with ample power. A gas-tight seal for the stirring s i a f t port is provided by bronze bellows bushing B. The vertical reflux condenser, C, is made of copper and is of the multiple water-tube type. The details of construction are more clearly shown in Figure 2. The condenser is about 4.5 inches in diameter and contains from forty-five to fifty 0.3125-inch copper tubes. The heights of the condensers vary from 18 to 48 inches; the taller ones are used for the more volatile reagents. The vapors are led through the lower condenser port t o the inner chamber where they circulate between the small tubes; the outer walls of these tubes and the inner wall of the inner shell provide ample condensing surface. Such condensers have proved efficient. The large capacity of the inner chamber provides ample storage space (2 to 4 liters) for the condensate in the event of flooding. The condenser is connected to the reactor by a sight glass, so that the rate of reflux may be observed. In the earlier models these were tubular and connected to the condenser and the reactor by stoppers. For later models the glass tubes have been replaced by bronze T-shaped tubes with glass windows, front and back, the connections being made by use of neoprene gaskets. Glass reactors give better visibility than metal ones and are ree from corrosion and catalytic effects, but the possibility of breakage introduces a definite fire hazard. Metal reactors, on the other hand, when equipped with effective stirring devices give rapid heat transfer and make possible better temperature control. The freedom from breakage greatly lowers the fire hazard. The present authors regard metal reactors as indispensable for batches of more than 10 moles and often prefer them for batches as small as 5 moles.
+
THE GRIGNARD REAGENT
In the preparation of alkylmagnesium halides, the alkyl chlorides may be used as well as the bromides or iodides. Methyl and ethylmagnesium chloride are the most difficult t o prepare. In practice the reaction is started with the bromide, the reactor cooled to 10" t o 25" C., and the gaseous chloride led in a t such a rate that little or no gas escapes through the condenser. If the gaseous chloride is introduced above the surface of the ether, vigorous stirring is essential t o ensure its rapid solution in the reaction mixture. More recently it has been the practice in this
+Cycloparaffins
I n some cases saturated hydrocarbons and alkyl substituted aromatic hydrocarbons are readily produced directly by a Wurtztype Grignard condensation.
609
.
INDUSTRIAL AND ENGINEERING CHEMISTRY
610
-Reaction Chamber -Bellows S e o l - R e t l u x Condenser -Water Jacket E-Stirrer F - Pipe Brockets G - Drain Valve H - L o a d i n g Hole I - Jacket Water Connections J- G e a r - h e a d Motor Clutch handle
Vol. 41, No. 3
Actual equivalency must be determined by testing for unused magnesium. As long as much magnesium is present., it may actually be heard as it is brushed against, the walls of the reaction vessel. When the amount remaining is small, it may be sampled by a long handled thief (an ordinary deflagrating spoon with an extra long handle will do). Such sampling is facilitated by the fact, that the residual magnesium is heaped a t t,he center on the bottom of the reactor by the swirling liquid when the stirring is stopped. When gaseous chlorides are used, final evidcnce of the completed reaction is the escape of gas through the condenser. In all cases the stirring is continued under reflux for a suitable pe-. riod. If convenient, this period may continue overnight. All of the components of the equilibriuni mixtures commonly known as Grignard reagents may not be in solution, but, including materials in suspension, the effective concentration of R--Mg--X should normally be 4 t'o 5 moles per liter. CONDENSATION
F
~
Figure 1.
.oratory to introduce the gas below the surface of the ether, in which case it is necessary to provide the inlet tube with a flexible thrust rod for clearing the tube in the event of plugging. The preparation of methyl and ethylmagnesiuni chlorides is greatly facilitated by the fact that these alkyl chlorides are readily available in commercial grades of high purity (refrigeration grade). The corresponding alkyl bromides and iodides also are obtained easily for use in initiation of the reaction. The high solubility of these chlorides in ether is also a n important factor. The usual run in a 15-gallon reactor is made with 60 gram atoms of magnesium and 12 to 15 liters of ether. Special synthetic ether (Carbide and Carbon Chemicals Corporation) is satisfactory for this purpose. Sometimes additional ether will need to be added during the preparation to keep the R-Mg--X in solution. Liquid alkyl halides are siphoned into the reactor from suitable reservoirs, with the aid of a slight positive nitrogen pressure, when needed. After the formation of the reagent is well started, the rate of addition of the halide is limited only by the cooling capacity of the reactor jacket and the reflux capacity of the condenser. In such cases it is advisable to run the reactor warm to ensure rapid reaction of the halide and to prevent its accuniulation in excess. The approximate point of equivalency may be determined by the weight of halide added. When gaseous alkyl chlorides are used, this weight may be measured by the loss in weight of the containing cylinder. Liquid alkyl chlorides are weighed out to be equivalent or in slight excess over the magnesium employed. It
.
Fifteen-Gallon Grignard Reactor
The condensation is carried out in the same reaction vessel. Liquid reactants are diluted with an equal volume of ether. The extra ether is added to the prepared Grignard reagent beforehand. if the react,ant to be added is a gas. Liquid carbonyl compounds such as aldehydes, ketones, and esters, react almost instantaneously and may be added as rapidly as the cooling capacity of the jacket a,nd condenser will permit. Gaseous reactants such as formaldehyde, acetaldehyde, and ethylene oxide may be introduced fairly rapidly into the free smce of the reactor without loss if the reaction mixture is cooled strongly arid stirred vigorously. Attempts to introduce such gases below the surface of the reaction mixture will generally result in plugging of the inlet tube, unless this tube is provided with a flpxible thrust rod foi cleaning. Aldehydes and ketones always reac? with one equivalent of R-Mg-X, whether by condensation, reduction, or enolization reactions. Carbonic. and carboxylic esters react with two equivalent5 of reagent, unless the alkyl group of the reagent is highly branched, or unless a low rpaction temperature is maintained. I n the case of ethylene oxide, the desired condensation does not occur a t once. It may be accelerated by the addition of a second mole of the oxide or by increasing the reaction temperature. The condensation proceeds slowly a t the reflux temperature of ethyl ether and under these conditions normally would be completed in some 10 days or 2 weeks. At higher temperatures the reaction is more rapid and may become uncontrollably violent. The usual procedure is to add a higher boiling solvent such a5 benzene, toluene, xylene, or n-butyl 4%" ether. The elhyl ether then id distilled from the reactor by circulating warm water or steam through the reactor jacket. The teniperature is gradually raised to the boiling point of the added solvent. Benzene is usually the mo51 suitable for this pulFigure 2. Tubular pose, since a fairly pure grade may be Reflux Condenser obtained cheaply; it is easy to recover, Water Flow and its r ~ f l u x ternpcrature (about -- - - Vapor Flow
. i
-
611
INDUSTRIAL AND ENGINEERING CHEMISTRY
March 1949
REACTIONS WITH KETONES TABLE I. GRIGNARD HzO (a) R&=O R-Mg-x > RaC-OMg-X -+ R,C-OH
(Initial products are tertiary carbinols; intermediate products are olefins or diolefins; and final products paraffins or cycloparaffins)
R-X
Vsed for
Operations
R-CO-R
R-Mg-x
I
+ b + fraction
n,-CIHa-Cl
CHa-CO-CHa
a
n-CdHa-Cl n-CaHv-CI n-CaHs-Cl I-CaHs-Cl a-GHg-CI 2-CaH7-Cl n-CsH,--Cl CZHJ-CI
CHs-CO-CH3 CHs-CO-CHzCHs CHa-CO-CHzCHs CHa-CO-CHzCHa CHs-CO-CHaCHa CH~-CO-CHZCHZCHB CH3-CO-CI-I(CHs)z CHs-CO-CHzCH(CHa)z
a + b + c a + b + c
CxHa-C1
+ + + + + +
CHr-CO-C(CHa)a
a a a a a a a
CHs-C1 CHr-C1 CHa-C1 CzHs-Cl CHa-C1
(CHs)zCH-CO--CH(CHa)v (CHs)zC=CH-CO-CHs (CHs)nC=CH-CO-CHs (CH~)~C=CH-CO--CHB CHzCHz-CO-CHzCHs
a a a a a
+ + + + +
C2Hs-Cl
CH~CHZ-CO-CHZCH?
a + b + c
Ethylcyclopentane
n-CaHs-Cl
CHzCHz-CO-CHzCHz
a + b + c
rz-Butylc yclopentane
CHs-C1
CH&H2--CO--CH&HaC€L
a + b
1 -Methylcyclohexene
n-CdHs-CI
CHzCHz-CO-CHzCHzCHz
a + b + c
n-Butylc yclohexane
CHa-C1
CHaCH-CHz-CO-CHzCHa
a + b + o
1,3-Dimethylcyclopentane
L-.----J
L--...-.-----d
L
-2
i
L
L------i
b b b b b b
+
+ + + + + +
o c c c c c
Hydrocarbons 2-Methyl-1-hexene 2-Methyl-2-hexene 2-Methylhexane 3-Methylhexane 3-Methylheptane 2,4-Dimethylhexane 3,4-Dimethylhexane 2,3-Dimet hylhexane 2,3-Di ~netliylhexane 2,4-Diinethylhexnno
+
+
b + c b b + c b + o b
80" C.) is a relatively safe temperature a t which to run the condensation reaction. At the boiling point of benzene the reaction starts slowly, generally with solidification of the reaction mixture; stirring becomes difficult, b u t is unnecessary a t this point. After the reaction is completed, the solidified reaction mixture may be softened or even liquefied by adding ether again. Wurtz-type condensations with a saturated halide proceed only slowly, and the reactant may be added quite rapidly. I n these cases it may be necessary t o continue t h e condensation for several days with stirring and at the boiling point of t h e solvent. Unsaturated compounds of t h e allyl type and the alkyl sulfates react a t intermediate rates, b u t must be added cautiously, since it is easily possible t o build up a n uncontrollable concentration. This is especially true since these condensations seem t o have an induction period. I n the Wurtz-type condensation R-Mg-X is consumed and RO-Mg-X is not formed. It is, therefore, possible t o follow the course of the reaction b y titrating the residual alkylmagnesium remains, more alkyl halide or sulfate halide. If much R-filg-X may be added advantageously t o react with it. If preliminary experiments indicate that the desired condensation proceeds to better advantage when the Grignard reagent is added to the other reactant, this may be accomplished by slowly siphoning the reagent from the reactor in which i t was prepared into another reactor containing the second reactant, or it may be drawn off into a suitable vessel for transfer. The transfer should be made in such a manner as t o protect the reagent from the air and t o avoid t h e spread of ether vapors. I n such operations nitrogen gas from a cylinder may be used t o apply a positive pressure, Alkyl magnesium chlorides and their condensation products are always prone t o solidify, hence powerful stirring and careful attention t o dilution are required.
2 3-Trimethylpentane { 22:3:3-Trimethylpentane 2,3,4-Trimethylpentane 2,4-Dimethyl-l,3-pentadiene 2,4-Dimethyl-Z-pentene 2,P-Dimethylhexane 1-Methyloyclopentene
5 parts\ 1 part ,
Yield,
?&
Literature References
5o
(17, 08) (08)
60
(09)
HYDROLYSlS OR QUENCHING
After the condensation is completed, the reaction product is decomposed in the reaction vessel. This procedure is to be strongly recommended, since it may be done under reflux with stirring and cooling, so t h a t the fire hazard is reduced to a minimum. The quenching may be done with dilute aqueous hydrochloric acid (in most cases diluted technical acid is satisfactory), ammonium chloride solution, or with water alone. When the final product is a tertiary alcohol, a minimum quantity of acid should be used in order to minimize the conversion of the carbinol t o the chloride or its catalytic dehydration and possible rearrangement, These undesirable reactions are largely avoided by the use of ammonium chloride solution for the hydrolysis. When the primary product is a n alcohol, the neutralization of basic magnesium salts requires approximately one equivalent of acid per gram atom of magnesium used. When the primary product is a hydrocarbon, as in t h e Wurtz-type condensation, little, if any, basic magnesium salt is formed on quenching, and less acid is required. I n the general case, toward the end of the hydrolysis, frequent tests for acidity should be made on samples withdrawn from the reactor; methyl orange, methyl red, and litmus paper are suitable indicators. WASHING AND STRIPPING
After the ether and water layers have had time to separate completely, the aqueous brine is withdrawn through the gate valve a t the bottom of the reactor. T h e ether solution of the reaction product is washed, while still in the reactor, and with stirring, first with water, and then with dilute sodium carbonate solution. This washing neutralizes any traces of acid remaining and removes the bulk of any low molecular weight alcohols present. When a suitable amount of saturated ammonium chloride solution has
'
INDUSTRIAL AND ENGINEERING CHEMISTRY
612
Vol. 41, No. 3
TABLE 11. GRIGNARD REACTIOXS WITH ALDEHYDES AND EPOXIDES R-Mg-X HzO (a) R-CH=O + R&H-OMg-X -+ R&H-OH (b) R2CH-OH
- HzO + CnHzn Catalyst
~
R’-Mg-X
(d) R-CH-CH-R L-OJ
> RCH(0-Mg-X)CHRR’
HzO -->
RC(0H)CRR’
( e ) RCH(OH)CHRR’ *+C,,H~, (f)
Catalyst HZ t R - C G H I O - C ~ H ~ ~ + I
R-c~H4-cnH2n-1
(Initial products are secondary carbinols: intermediate products are olefins: and final products p a r a 5 n s , aromatics, or cycloparaffins) R-X Used for
R-Mg-X
R-CHO
Operations
t-C4HP-C1
CHs-CIIO
a
+ b + fraction
I-CIHs-Cl
CHaCHz-CHO
a
+ b + fraction
t-CaHs--Cl
CHaCHzCHa-CHO
a
+ b + fraction
t-CaHs-Cl
CHaCHzCH3-CHO
a
a-CaHs-Cl
CIL-CHz LOJ
n-CdHs-Cl
(CH3)zCH-CHO
n-CaHr-C1 CaHs-Br CaHs-Br
CaH6CHO CHaCHaCH-CHO (CHa)nCH-CHO
n-CaHr-C1 CsHs-Br CaHs-Br CaHa-Br &Ha-Br
CaHsCHO CHaCHzCHz-CHO (CHa)aCH-CHO CHaCHzCHz-CHO (C1la)zCH-CHO
a
Hydrocarbon 3 3-Dimethyl-1-butene 2’3-Dimethyl-1-butene 2:3-Dimethyl-2-hutene 4,4-Diinethyl-2-pentene 2,3-Dimethyl-l-pentene 2,3-Dimethyl-Z-pentene 2,2-Dimcthy1-3-hexene 2,3-Dimetliyl-l-hexene 2,3-Dimethyl-Z-hexene
Yield,
Literature References (81,100)
%
6 parts 4 parts 1 part 3 parts 2 parts 1 part
TI::
1
!
2 parts
30
($1, 100) (81, 100)
(91)
40
(83, 4%)
(48. 27) (80, 48)
50
(61.
4.8)
+ b + fraction + o d + e + fraction
2,Z-Dimethylhexane 2,3-Dimethylhoxane
40
(43, 4.8) (66.48) (26,10.8)
3-Methyl-1-pentene
20
(76)
a + b + c a b fraction a b fraction b fraction a a b fraction a b fraction a b fraction b fraction a a b fraction
2-Methylheptane 1-Phenyl-1-butene I-Phenyl-i-butene I-Phenyl-2-methylpropene n-Butylbenzene n-Butylbenzene Isobutylhenzene n-Butylcyclohexane Isobutylcyclohexane
45
(6,
30
[YO (39, 7 l ) l
+ + + + + + + +
++ + + + + + +
++ + +f +f
a
2 parts
3 parts)
f4)
..
(‘YO,48) (87, 49)
25
[‘YO (3’9, 7 1 , 78) (70) (75) (86, 88) ($3, 82)
40 25
35 30 35
Selective hydrogenation.
REACTIONS WITH ESTERS AND ANHYDRIDES TABLE111. GRIGSARD (a)
R-COO-R
R’Mg-x
(b) R-CO-0-CO-R
(e)
> RR’2C-OH R’Mg--X
+
RR’zC-OH
Cntyped reaction
(Initial products are tertiary carbinols or esters; intermediate products are olefins; and final products are paraffins) Yield, R’-X Used for R ’- M g-X R-COOR Operations Hydrocarbons or Intermediate % 4-Rlethylheptane 35 a + c + d n-CsHT-Cl CI-I~--COO-C~Hs 4-iitethglheptane 35 a + d + c + d CHa-CHCHz-Cl CHa-COO-CzHs 3-Et hyl hexane n-CaH,-COO-C2Hs a + c + d CzHs-Cl 2-Methyl-3-ethylpentane i-CsHi-COO-CzHs a + c + d Cz Hs- C 1 2-Met hyl-3-ethylpentane (CzHa)CH-COO-CzHr a + c + d CHa-C1 CHI-CI
i-CaHr-COO-CHs
a + c + d
2:3-Dirnethyl-Z-butene 2 3-Dimethyl-I-butene
GHs-0-COO-CzHs
e
Ethyl trimethylacetate Ethyl trimethylacetate 2,3,3-Trimethyl-l-butene 2,2,3-Trimethylbutane Ethyl 2,Z-dimethylbutyrate 2,3.3-Trimethylpentane 2,2,3-Trimethylpentane 3-Ethyl-2-pentene 3-Ethylpentane
e
t-CbHn-Cl
C1-COO-CsHs (CHa)aC-COO-CzHa (CHa)G-COO-CzHs c02
CHr-C1
CZH~(CHJ)~C-COO-C~HS
+ a + c + d + fraction
C2Hs-Cl CzHs-C1
C~H~-CO-O-CO-CzHs C2Hs-CO-O-CO-CzHa
b + c b + c + d
a + c a + c + d e esterification
{
45
..
Literature References ( 1 % 6) (18,6)
(81, 100)
(Si,100)
.....
35 30 45
(Zi,’i+)
20 5 80 60
(98)
(8, 102)
.....
( 1 7 , 88) ($7) (69.67)
March 1949
INDUSTRIAL AND ENGINEERING CHEMISTRY TABLEIV.
613
GRIGNARD REACTIONS WITH ALKYLHALIDES AND SULFATES (a) R’-X
R-Mg-X
f
R’-R
(Initial products are paraffin hydrocarbons) R-X Used for R-Mg-X CzH6-Cl n-CsH7-Cl iGHv-CI CzH6-CI CsHs-‘21 CzHa-C1 f-C4Hs-C1 n-CaHii-CI i-CsHii-CI
R’-X
Operations a a a a a a
t-CsH11-Cl
t-C4Hs--CI n-CaHii-C1 i-CsHii-CI
Yield,
%
Hydrocarbons 3,3-Dimethylp?ntane 3,3-Dimethylhexane 2,3,3-Trimeth lpentane 3-Methyl-3-et~ylpentane 3 3-Diethylpentane 2:2,3,3-Tetramethylpentane
30 30 35 50
40
20
(Recovered by-products of Grignard reagent formation) a 2,2,3,3-Tetramethylbutane n-Decane a 2,7-Dimethylootane a
5
5 5
:Initial product is a n aromatic hydrocarbon) b 1 2-Dimethylbenzene 1:4-Dimethylbenzene b b 1-Methyl-2-ethylbenzene b I-Methyl-3-ethylbenzene b I-Methyl-4-ethylbeneene
Z-CHa-CeHa-Br
(CHd)2SOa
65
55 50 GO 55
(Initial product is an aromatic, final product a cyclohexane) irans-l,2-Dimethylcyclohexane b + o cis-1,2-Dimethylcyclohexane
GO
tran.9-l,4-Dimethylcyclohexane cis-1,4-Dimethylcyclohexane
50
4-CHz-CsHa-Br
b f c
been used, washing is unnecessary as the by-product magnesium compounds precipitate from the ether solution of products: After the wash solutions have been withdrawn, the ether solution of the reaction product is run into 5-gallon glass bottles for storage, pending the stripping of the ether. The ether is removed from the reaction product by distillation through a column of suitable efficiency. When the product has a high boiling point, a simple one-plate distillation is adequate If the product is a low boiling hydrocarbon, fractionation a t relatively high efficiency is indicated to remove the ether. I n a few cases, as when a high boiling medium such as n-butyl ether has been used, the product may be distilled as a forerun from the solvent. EXTENDED REACTIONS
After the solvent has been removed, the product should always receive further purification to separate it from residual reactants and by-products. The more stable alcohols are usually sufficiently pure after a single fractionation. Many alcohols are converted to the corresponding chlorides or bromides and carried through a n additional Grignard reaction. I n the usual case, however, the alcohol is dehydrated to an olefin or a mixture of olefins. For many alcohols this dehydration may be carried out in such a manner that the olefins have the same carbon skeleton as the carbinol from which they were derived. Other alcohols of the neopentyl type give both normal and rearranged olefins because of a predictable migration of an alkyl group; the extent of the rearrangement depends on the conditions of dehydration. I n the case of easily dehydrated (tertiary) carbinols, the dehydration may be carried out on the crude product, but efficient fractionation of the olefins should follow. Olefinic alcohols may be dehydrated to give diolefins, and aromatic alcohols to give phenylolefins. Any hydrocarbon derived from a n alcohol in this manner may be taken either as a final product in itself, or it may be hydrogenated t o the corresponding paraffin, aromatic, or cycloparaffin. Many hydrocarbons emerge directly from the Grignard reaction and need only simple treatment t o attain high purity. I n other cases mixtures are produced which require highly efficient frac-
} }
tionation and/or other special techniques to effect a separation. Again, the primary product may represent merely a n intermediate in an extended synthesis: A mono-olefin may be rearranged into an isomer with the double bond in a different position, or an unconjugated diolefin or phenylolefin may be rearranged into the corresponding conjugated hydrocarbon. Unsaturated hydrocarbons of all types may be hydrogenated to the corresponding paraffins or cycloparaffins. HYDROGENATION
Hydrogenation, in the usual case, is carried out catalytically in a high pressure rocking autoclave (of the type made by the American Instrument Company). It is always advisable t o explore t h e hydrogenation of any new unsaturate by using small quantities in a small bonit, until its hydrogenation characteristics are well understood. It then will be possible t o proceed t o bombs of a large capacity for the purposes of production. Xckel on kieselguhr is ordinarily used as the hydrogenation catalyst. I n most cases pressures of from 1000 t o 2500 pounds per square inch and temperatures from room temperature up to 250” C. are effective. When the unsaturate is particularly resistant to hydrogenation, or because marked instability requires hydrogenation a t low temperatures, a more active catalyst, such as Raney nickel, is used. Residual unsaturation is one of the more common and more persistent impurities in saturated hydrocarbons. Repeated hydrogenation over fresh, active catalyst is an effective and economical method for its removal. Repeated agitation with an aqueous solution of potassium permanganate is also effective. PURIFlCATION
A hydrocarbon should receive a preliminary fractionation to remove the bulk of the grosser impurities. It then should be dehalogenated completely before any attempt is made at final fractionation or hydrogenation. Dehalogenation may be accomplished by agitation with hot alcoholic alkali or with sodium in liquid ammonia solution. I n this laboratory the latter process is preferred; it is both rapid and effective. Sodium in ammonia
INDUSTRIAL AND ENGINEERING CHEMISTRY
614
Vol. 41, No. 3
GRIGNARD REACTIONS WITH ALLYLICHALIDES R'-Mg-X (a) R&-C(R)CH,-X .-z RnC=C(R)CIIpR (R-H or C&) TABLEV.
H2 (b) R2C=C(R)CH*R' Catalyst 1
C)
RzCHCH(R)CHZR'
H
CBH,-CH-C(R)CH~
CsH,-CH2C€I(R)CH,
,d) COH~-CH&K(R)CHs ~atalyst H2 -f CsHIl-CH2CH( R) C tl3 (Initial products are mono-olefins, diolefins, cyclo-olefins, or aryl olefins; secondary products are pawfTins, cycloparaifini, or aromatics) Yield, L i t a r a t u r r .\llylic Halide Operation Hydrocarbon yo Referenr.r, 4-Methyl-1-pentane a 45 4,4-Dlmethyl-l-pentene a 40 22-Dimethylpentane t-CaHs-C1 a + b 40 1-Octene n-CsHu-CI a 70 n-Octane n-C&Hw-CI a f b 60 i-CbI-Ill-CI 6-1\Iethyl-l-heptene a 60 3,3-Dimethyl-l-hexene I-C6HIi--Cl a 20 1.S-Hexadiene CHz=CHCHJ---Cl 50 n-Hexane 60 t + b CHz=CHCHz-Cl I-Methyl-4-allylbenzcne a 4-CHs-CsHa-Br 40 me a f rearrsngernrnt c l-;\Iethyl-4-(n)-propylbenzt 4-CHs-CsHr-Br 35 2,4-Dimethyl-l-pentene 8. 2-Methyl-1-heptene a 2-Methyl-2-heptene n rearrangpinens 2,4,4-Trimethyl-l-pentene ~$-CaHs-Cl CHz=C( CH3) CHz--Cl a 2.5-Dimethvl-1 .Lhexadiene CHz=C(CHs)CH*-Cl CH2-C(CHs)CHz-C1 a C Ha= C (CHs) C Hz-C1 C Hz=C ( CHI)CHz-'21 2;6-Dimeth$l-2;4-hexndicne a reat't'angeiiient CIL=C(CHs)CHz--.Cl 2.5-Dimethvlhexa ne CH~=C(CFII)C H - C l a-tb CaHs-Br CEHK-B~ 45 &G; 88)
R'-X Used for R'-Mg-X
+
+
+
n-CdHI--CI
CH,CH?CH=;C€ICB--Cl
a
3-(n)-Prnpylcyclopent~ne
35
(82)
n-C.5II;--CI
CHzCI-IzCH=CHCH -~-C1
a + b
n-Propylcyclopentane
85
(28, 7 !
i-CsH7-CI
CHzCHzCH=CHCR-41
J
3-Isopropyloyclopentene
20
(82)
i-CsHi-CI
CHzCHzCH=CHCH--. C1 L -3
a ib
Isopropylcqclopentane
20
(18)
~-CIH~-CI
CH&H=CHCH?
I
L-
L___--_I
J
i
GI CL.I:CHII:"H=CH~]
R
+ fraction
2-Octene 3-Methyl-1-iieptene
(36,4 1 )
C1. C-C~HB-CI
e-CsHr-CI
*
CH3CFI=CE€CH2
1
CICH3bHCH=CHg]
CHJC=CHCH-CL~CH~~CH=CH*
a
+ fraction
a
+ fraction
6-Methyl-2-heptene 3,5-Dimethyl-l-hexene}
2-Methyl-2-heptene 3,3-Dirnethyl-l-hexene
C"s
a0
(85,4 1 )
3 parts) 4o :part ,
8 4 , 41) (7%)
Either a catalyst under selective Iiydrogenrttion condition8 or a selective chemical reagent may be used.
,converts alkyl halides t,o hydrocarbons (or amines) and aldehydes, ketones and esters to alcohols (or other products) which boil well outside the range of the desired hydrocarbon. Occasionally a hydrocarbon is contaminated by an alcohol with which it forms a n azeotrope. If this cannot be removed by washing with water, it may be necessary to agitate the azeotrope with dry sodium amide and filter or distill t o eliminate the alcohol as its solid sodium derivative. Filtration through a column of silica gel, or refluxing with sodium, may be indicated for removal of the last traces of moisture or other polar impurities. The silica gel treatment must be used with caution as it is known t o induce rearrangemelit and polymerization of sensitive olefins and diolefins. \\'here these possibilities are suspected, the silica gel filter tube should be chilled hy dry ice during the filtration. Fractional distillation of the final product present's many difficulties in the product,ion of hydrocarbons in quantity and in high purity. The distillation is an essential step, however, even when the starting materials are pure and the procedures arc selected for specificity, but varying efficiencies are needed. The requirements may be met, suitably, by Fenske-type packed columns of various diameters and heights, and by a considered choice between straight or azeotropic dist,illation.
In such fractionat,ions precautions should be taken against volatilization losses. If t,he product is unsaturated, precaut,ions should be taken against peroxidatiori losses also. The vapor surface in the column should be prot,ected by a slow stream of nit,rogen, and the receivers should be filled wit,h the same gas. Fraction bottles should be tightly st,oppered and stored a t a low temperat,urc t,o minimize volatilization and polymerization. The advances in the methods of fractionation, which have bocri made during the last fex years, have made possible like advances in the criteria of purity. It has become the common practice in this laboratory to measure and record not only the boiling point and refractive index curves, but, also the density and freezing points of numerous fractions. Those fractions which occupy a constant plateau for all properties should be combined and taken as the product. In cases where the cryoscopic behavior of the product is suitable, the freezing point, (melting point) is used rn the final crit>erionof purity. TABLES
Tables I t o V summarize the use of the Grignard reaction in eight different types of condensation. Generalized equations
INDUSTRIAL AND ENGINEERING CHEMISTRY
March 1949
6 18
TABLE VI. PHYSICAL PROPERTIES OF PURIFIED HYDROCARBOSSO {.I’
Hydrocarbon
d.‘
O
B.P., C./760 Mm.
d’:
ny
F P
Hydrocarbon
O.6:
PARAFFINS n-Hexane 3-Ethylpentane 2-Methylhexane 3-Methylhexane 2 %Dimethylpentane 3:3-Dimethylpentane 2,2,3-Trimethylbutane n-Octane 2-Methylheptane 3-Methylheptane 4-Methylheptane 3-Ethylhexane 2,2-Dimethylhexane 2 ,a-Dimethylhexane 2,4-Dimethylhexane 2,5-Dimethylhexane 3 3-Dimethylhexane 3:4-Dimethylhexane 2-Methyl-3-ethylpentane 3-Methyl-3-ethylpentane 2 2 3-Trimethylpentane 2:3:3-Trimethylpentane 2 3 4-Trimethylpentane 2’2’3 3-Tetramethylbutane 3:3:diethylpentane 2,2,3,3-Tetramethylpentane n-Decane 2,7-Dimethyloctane
-95.39 -118.76 -118.24 glass 123.85 -134.98 -25.06 -56.56 -109.58 -120.80 -121.09 glass glass glaw glass -91.49 glass glass -115.18 -90.93 -113.3 -102.4 -109.32 flOl -33.25 -10.0 -30.26 -54.6
-
68.68 93.45 90.05 91.88 79.18 86.05 80.85 125.6 117.63 118.89 117.63 118.7 106.86 115.5. 109.8 109.3 111.9 118.0 115.55 118.28 110.0 114.7 113.8 106.5 146.20 140.25 174.12 159.87
0.65933 0,6982 0.6787 0.6871 0.6739 0.6933 0.68999 0.70272 0.6981 0.70583 0.70464 0.7128 0.6954 0.7125 0.7002 0.6939 0.7103 0.7185 0.71930 0.72744 0.7156 0.72681 0.7182
1.37475 1.3938 1,3850 1.3888 1.3822 1.3910 1.38936 1,39747 1.39497 1.39849 1.39783 1,4021 1.3940 1.4020 1.3951 1.3929 1.4007 1.4041 1.40402 1.40775 1,4029 1,4079 1.40417
3-Methyl-1-pentene 4-Methyl-1-pentene 3,3-Dimethyl-l-butene 2 3-Dimethyl-2-butene 2:Methyl-2-hexene 2,4-Dimethyl-l-pentene 4,4-Dimethyl-l-pentene 2,3-Dimethyl-Z-pentene 2,4-Dimethyl-a-pentene 2,3,3-Trimethyl-l-butene 1-Octene 2-Octeneb 2-Methyl-1-heptene 6-Methyl-I-heptene 2-Methyl-2-heptene 6-Methyl-2-heptene b 2,3-Dimethyl-l-hexene 2 3-Dimethyl-2-hexene cjs-2 2-Dimethyl-3-hexene
0:7536 0.7568 0.7309 0,7242
1.4205 1,4232 1.4122 1.4086
1-Methylcyclopentene 3-n-Propylcyclopentene 3-Isopropylc olopentene I-Methylc yc36hexene
0.76658 0.7460 0.77637 0.77662 0.7846 0.79658 0.77567 0,7827 0.76257 0.7994 0.7953
1.41967 1,4095 1.42617 1.42570 1.4315 1.43591 1,4271 1.4299 1.42080 1.4409 1.4388
1,5-Hexadiene 2 4-Dimethyl-1 3-pentadiene
trans’-2,2-Dimethyl-3-hexene 2.4,4-Trimethyl- 1-pentene
trans-1,4-Dimethylcyolohexane n-Butylcyclohexane bobutylcyclohexane
-138.46 -140.6 -117.52 -111.53 -107.99 -50.18 -88.6 -86.7 -36.94 -74.85 glass
103.45 91.05 130.92 126.40 156.60 129.84 123.7 124.5 119.33 180.94 171.29
54.18 54.00 41.23 73.19 95.41 81.64 72.1 97.34 83.31 77.9 121.27 125.2 119.3 113.19 122.6 117.7 110.54 121.85 105.8 100.9 101.44
CYCLO-OLPFXNS -127.0 75.8 125.9 121.2 -1ii:o 110.3
....
. ...
CYCLOPARAFFINS Ethylcyclopentane 1,3-Dirnethylcyclopentaneb n-Propylc yolopentane Isopropylc yclopentane n-Butylo yclopentane cis-1 2-Dimethylcyclohexane tran~-1,2-Dimethylcyclohexsne cis-l,4-Dimethylcyclohexane
OLEFIN8 - 154.55 -154.01 -115.07 -74.54 glass -123.98 -136.7 glass glass -111.9 -102.0 -94.0 -90.14 glass glass glass glass glass glass glass -93.74
B.P., C./760 Mm.
d:’
ng0
0.6675 0,6639 0,6530 0.7081 0.7081 0.6943 0.6827 0.7269 0.6950 0.7048 0.7151 0,7192 0.7206 0.71195 0.7241 0.7152 0.7210 0.7405 0.7186 0.7040 0.7149
1.3840 1,3830 1,3760 1.4123 1.4103 1.3986 1.3918 1.4211 1.4038 1,4030 1,4090 1.4130 1.4120 1.4067 1.4172 1,4110 1.4111 1.4269 1.4099 1.4063 1,4085
0.7802 0.7910 0.7941 o.8101
1.4330 1.4359 1.4380 1.4501
DIOLEFINS
4 Eight hydrocarbons appear in the production-yield tables which do not appear here. These compounds,were not isolated in a state of purity high enough to permit the determination of accurate ph siaal propertipa. b Physical properties listed were measured on d e cis-trans mxture produced by the reaction shown in the production-yield tables.
for the condensation and the subsequent reactions have been inserted in the tables. References to the literature have been limited to the article giving the first significant description of the hydrocarbon and t o those using the same, or an analogous method, of preparation. Where only one reference is given, either the first method was similar to that used in this laboratory, or no analogous method could be found in the literature. The yields in column 5 have been rounded off to the nearest multiple of 5%. The yields in a large number of runs will vary and those shown are not the highest, but represent fair average values. The freezing point (’ C.), boiling point ( O C./760 mm.), density d?’), and refractive index (ng) for 79 hydrocarbons prepared by the procedures described are shown in Table VI. The values shown are the best obtained for the respective hydrocarbons in this laboratory. They compare favorably with the selected values of the American Petroleum Institute Research Project 44 which has carried out a critical survey of the physical properties of hydrocarbons of all types. Freezing points (melting points) and standard boiling points were measured with a platinum resistance thermometer in connection with a Mueller resistance bridge (Leeds and Northrup, Type G-2). This thermometer was calibrated a t the National Bureau of Standards. The apparatus used in determining freezing and melting points was essentially that described by Mair and his co-workers (66)a t the National Bureau of Standards. The appratus used in determining standard boiling points was the same as that described by Quiggle, Tongberg, and Fenske (69) and was connected to a manostat which maintained a pressure equal to 760 mm. of mercury; nitrogen gas was used to Supply a positive pressure.
2:6-Dimethvl-l:5-hexadiene
1.2-Dimerhylbenzene 1.4-Dimethylbenzene l-hl~thyl-2-~thylhenrene 1-Met hyl-3-ethylbenaene 1-hlcthyl-4-ethylbenzene n-Butylbenzene Isobutylbenzene 1-Methyl-4-propylbenzene 1-Phenyl-I-butene 1-Phenyl-2-methylpropene I-Methyl-4-allylbenzene
....
-116.0 -75.6 +13.66
82.0 93.73 114.3 134.5
0.7242 0.7369 0.74230 0.7615
1.4535 1.4412 1.4290 1.4781
AROMATICS -25.23 f13.15 -81.02 -98.04 -63.24 -88.15 -51.54 -64.20 -43.06 -51.18 -44.71
144.46 138.35 165.14 161.29 162.00 183.26 172.92 183.46 198.68 187.91 182.91
0.8800 0.8609 0,8806 0.8846 0.8614 0.8601 0.8532 0.8582 0.9019 0.9011 0.8799
1.50521 1.49570 1.5043 1.4965 1.4950 1.4900 1.4865 1.4922 1.5420 1.5397 1.5091
Refractive indexes were measured on an Abbe refractometer connected to an electronically controlled constant temperature bath. Densities were measured with 20-ml. pycnometers, carefully calibrated and checked by several members of this laboratory. The constant temperature bath for these measurements was regulated to within 0.02’ C. ACKNOWLEDGMENT
This work was carried out under the sponsorship of the American Petroleum Institute and the Ohio State University Research Foundation. Sincere appreciation is expressed for the guidance and counsel of the Advisory Committee of the American Petroleum Institute Research Project 45, the present members of which are: R. F. Merschner, chairman, L. C. Beard, Jr., F. E. Frey, W. A. Herbst, W. G. Lovell, and Louis Schmerling. The following members and former members of the research staff of t h e American Petroleum Institute Research Project 45 actively participated in the work described in this paper: A. P. Lien, J. Donald Gibson, Frank W. Haeckl, John B. Beltz, Louis C. Gibbons, Grant Crane, John h4. Butler, Robert H. Arrowsmith, Harry E. Risher, Gerald T. Leatherman, Henry H. Chanan, Robert W. Shortridge, Amos Turk, Jules I. Shapiro, Thomas H. Newby, Edgar A. Cadwallader, Melvern C. Hoff, Walter C. Edmisten, T. Phillip Waalkes, and Thomas S. Hodgson. LITERATURE CITED
(1) Barbier, p., and Grignard V., Bull. sac. chim., [3] 31,840 (1904). (2) Bert, L., Compt. rend., 180, 1506 (1925). (3) Roord, C. E., “Science of Petroleum,” Vol. 11, Sec. 20, pp. 1349-56, London, Oxford University Press, 1938.
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Bouis, J., Ann. chim. phys., [3J 44, 77 (1855). Buelens, A., Rec. truv. chim., 28, 118 (1909). Butler, J. hl., and Boord, C. E., Ohio State Univ., Abstracts Doctoral Dissertations, No. 34, 85 (1941). Chavanne, G., and Beokqr, P., Bull. S O C . chim. Belges, 36, 591 (1927). Chavanne, G., and L.jeune, B., Ibid., 31, 9X (1922). Chavanne, G., and Miller, O., Zbid., 39 287 (1930). Chavanne, G., and deVogel, L., Ibid. 37, 141 (1928). Clarke, L., Am. Chem. J., 39,572 (1908). Clarke, L., Be?., 40, 352 (1907). Clarke, L., J. Am. Chem. SOC.,30, 1144 (1908). Zbid., 31, 107 (1909). Zbid.. n. 58.5 (19091. Ibid., $3, 520'(1911). Ibid., 34, 170 (1912) Clarke, L., and Riegel, E. I.,Ibid., p. 678. Claus, b.,and Mann, F., Ber., 18, 1121 (1885). Cortese, F., J . Am. Chem. Soc., 51, 2266 (19291. Couturier, F., Ann. chim. phys., [6]26, 459 (1892). Crane, G., Boord, C. E., and Henne, A. L., J . Am. Chem. Soc 67, 1237 (1945). Dietrich, M. A., and Boord, C. E., Ohio State Univ., Abstracts Doctoral Dissertations, KO.14, 12 (1934). Dolliver, hl. A . , et al., J . Am. Chem. ~ o c . 59, , 832 (1937) Douris, R., Compt. rend., 157, 55 (1913). Dykstra, H. R..Lewis, J. F., and Boord, C. E., J . Am. C h e m , Soc., 52, 3396 (1930). Edgar, T. A. G., Calingaert, G., and Marker. R . E., Ibid., 51. 1483 (1929). Eisenlohr, F., and Gore, G., Fortschr. Chem. Ph&k u . physili. Chem., B18, No. 9. 10 (1925). Eltekow, A , , Ber., 16, 39.5 (1883). Engler, C.. and Halmai, B., I b i d . , 43, 397 (1910). Favorski, A., and Alexejeiva, V., J . Russ. P h y s Chem. Soc., 50 561 (1920). Fittig, R., and Bieber, P., Ann., 156, 238 (1870). Fittig, R., Schaeffer, C., and Konig, J.,I b i d . , 149, 334 (1869). Friedel, C., and Ladenburg, A., Z b i d . , 142,310 (1867). Gibson, J. D., and Roord, C. E., Ohio %ate Univ., Abstracts Doctoral Dissertations, No. 28, 117 (1939) Gilman, H., and Hoyle, R. E., J . Am. Chem. SOC.,44, 2623 (1922). (37) Glinzer, E., and Fittig, R., Ann., 136, 303 (1865), (38) Zbid., 156, 312 (1870). (39) Grignard, V , Ann. chim. phys., [ 7 ]24, (1901). (40) Grignard, 1' , Ann. Univ. Lyon, VI 1-116 (1901). (41) Henne, A. L., Chanan, H., and Tuik, A . , J . Am. Chem. Soc., 63,3474 (1941). (42) Henne, A. L., and Matuszak, A., I b i d . , 66, 1649 (1944). (43) Horney, A . G., and Boord. C . E , Ohio State Cniv., Abstiacts Doctoral Dissertations, No. 23, 101 (1937). Howard, F. L., Brooks, D. B., et al., Aiatl. B u r . Standards, Sp3c. Rept. to N.A.C.A. Sub-Commit,tee on Airrraft Fuels and Lubricants (July 23, 1942). Hurd, C. D., and Bollman, 1%.T., J . Am. Chem. Soc., 55, 699 (1933). I b i d . , 56, 447 (1934). Just, F., Ann., 220, 154 (1883). Kaschirsky, M ., Rer., 11,984 (1875). IZlages, A., Ibid., 37, 1723 (1904) Kolbe, H., Ann., 69, 261 (1849) Kuvkendall, S . B., and Boord. C. E., Ohio State Univ., Abstracts Doctoral Dissertations. N o . 17, 241 (1935). (62) Lachowicz, B., Ann., 220, 168 (1883). (53) Ladenburg, A . , Ber.. 5 , 752 (1872). (54) Lien, A . P., and Boord, C. E., Ohio State Univ., Abstracts Doctoral Dissertations N o . 36, 193 (1942). (55) Mair, B. J., Glasgow, A R . , and Rossini, F. D., J . Research Nail. Bur. Standards, 26, 591 (1941). (66) Marker, R. E., and Oakwood, T. S., J . Am. Chem. SOC.,60, ~
Vol. 41, No. 3
(69) Quiggle, D., Tongberg, C. E., and Fenske, M. R., IND.ENO. CHEII., ANAL. ED.,6, 466 (1934). (70) Radziseewski, B., Be7., 9, 261 (1876). (71) Ramart, P., and Amagat, P., Snn. C h i m . phys., [ 8 ] 10, 306 (1927). (72) Reid, R. J., and Boord, C . E., Ohio State Univ., Abstracts Doctoral Dissertations, No. 27, 119 (1939). (73) Riess, J., B e y . , 3,779 (1870). (74) Risseghem, H. van, Bull. soc. chim. Belges, 35, 3286 (1926). (75) Ibid., 39, 349 (1930). (76) Rudel, H. W., and Boord, C. E., Ohio State Univ., Abstracts Doctoral Dissertations, No. 28, 253 (1939) (77) Sabatier, P., and Senderens, J. B., Compt. rend., 134, 1129 (1902). (78) Schluback, H., and Miedel, H., Be?., 57, 1684 (1924). (79) Schmitt, J., and Boord, C. E., J . Am. Chem. Soc., 54, 751 (1932); 53, 2427 (1931). (80) Schurman, I., and Boord. C. E., Ihid., 55, 4931 (1933). (81) Shoemaker, B. H., and Boord, C. E., Ihid., 53, 1505 (1931). (82) Signaigo, F. K., and Cramer, P. L.,Ibid., 55, 3326 (1933). (83) Soday,F. J., and Boord, C. E., Ihid., p. 3293. (84) Spath, E., Monatsh., 34, 1982 (1913). (85) Swallen, L. C., and Boord, C. E., J . Am. Chem. SOC.,52, 651 (1930). (86) Tafel, J., and Jurgens, W., Ber., 42, 2548 (1909). (87) Tiffeneau, T., Ann. chim. p h y s . , [SI 10, 365 (1907). (88) Tuot, M.,Compt. rend., 197, 1434 (1933). (89) Tuot, &I.,and Meyer, A , , Ibid., 196, 1231 (1933): 197, 1434 (1933). (90) F'ogel, A. I., J . Chem. Soc., 1938, p . 1323. (91) Waterman, H. I., De Kok, W.J. C., Rec. tmv. chim., 52, 234 (1933). (92) Ibid., 53, 727 (1934). (93) Werner, A, and Zilkens, F., Ber., 36, 2117 (1903). (94) Whitmore. F. C., and Evers, W. L., J . Am. Chem. SOC.,55, 813 (1933). (95) Whitmore, F. C., and Herndon, J.M., Ibid., p. 3428. (96) Whitmore, F.C., and Homeyer, A. H., Ihid., p. 4555. (97) Whitmore, F. C., and Jlouk, A. L., Ihid., 54, 3714 (1932). (98) Whitmore, F. C., and Laughlin, K. C., I b i d . , 54, 4011 (1932); 55, 2607 (1933). (99) Zbid., 54, 4392 (1932); 55, 2607 (1933). (100) Whitmore, F. C., and Meunier, P. C., I b i d . , 55, 3'721 (1933). (101) Whitmore, F. C., and Wrenn, 9. N.,I b i d . , 53, 3136 (1931). (102) Wibaut, J. P., et al., Rec. trav. chim., 59, 329 (1939). (103) Wroblewski, E., Ann., 192, 198 (1878). (104) Wurtz, A., Ann. chim.phys., [3] 44, 275 (1886). (105) Zander, A., Ann., 214, 148 (1882). (106) Zelinsky, N. D., Ber., 30, 387 (1897). (107) Zelinsky, N. D., J . Russ. P h y s . Chem. SOC.,38, 625 (1905). (108) Zelinsky, N. D., and Preewalsky, E, C., Ibid., 39, 1168 (1907). RECEIVED June 20, 1946. Presented before the Division of Petroleum Chemistry a t t h e 110th Meeting of the AIMERICAX CHEUICALSOCIETY, Chicago, Ill.
2 R R_ R I 1.F )_ R~~, R). _ ~~
(57) (58) (59) (60)
Markownikoff, V., Ann., 307, 335 (1899). Markownikoff, V., Be?., 33, 1905 (1900). Markommikoff,T'., J . R i m P h y s . Chem. Soc., 36, 58 (1904). Mavity, J. M., and Boord, C. E., Ohio State Univ., Abstracts Doctoral Dissertations, A-0. 7, 197 (1931). (61) hlereshkowski, E . , J . Russ. P h y s . Chem. Soc., 45, 1940 (1913). (62) Morgan, G. T., Carter, S. R., and Duck, A . E., J . Chem. Soc., 127, 1252 (1925). (63) Moslinger, W., An.%., 185, 49 (1877). (64) Muset, J., Bull. acad. roy. Delg., 1906. p, 775. (65) Noller, C. R., J . Am. C h e m . Soc., 51, 594 (1929). (66) Norris, J. F., and Green, E. H., Am. Chem. J . , 26, 313 (1901). (67) Przibytek, S. A., Ber., 20, 3240 (1887). (68) Przibytek, S. A., J . Russ. P h y s . Chem. SOC.,20, 507 (1888).
COURTEBY, PHILLIP6 PETROLEUM COMPANY
Precision Fractionation Equipment for M a n u f a c t u r e of Pure Hydrocarbons
