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Патент USA US3046324

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United States Patent O?iice
Ellis K. Fields and .loseph M. Sandri, Chicago, ilh, as
signors to Standard Oil Company, Chicago, iii, a cor
poration of Indiana
No Drawing. Filed 0st. 30, 1959, Ser. No. 849,751
5 Claims. (Cl. 260-650)
Patented July 24, 1962
The novel compounds of this invention having the for
mula hereinbeiore set forth include compounds whose
Ar-groups are not appreciably more acidic than are the
aryl hydrocarbon groups such as phenyl, tolyl, ethyl
phenyl, cumyl, the monobutylphenyls, xylyl, diethyl
phenyl, diisopropylphenyl, cymyl, naphthyl, methyl
naphthyls, ethylnaphthyls, biphenyl, .alkylated biphenyls,
vinylphenyl, a-methylvinylphenyl, and the like. The Ar
This invention relates to a novel class of substituted
group may contain a single aromatic ring as in the phenyl,
aromatic compounds, the 1-a~ryl-2,2-dihalocyclopropanes
and l-aryl-1-methyl-2,Z-dihalocyclopropanes and especial
ly pertains to l-aryl and l-aryl-1-methyl-2,2~dichloro-V
10 alkylated phenyls, phenylene, etc. groups, two or more
and 2,2-dibromo-cyclopropanes and a process for prepar
ing them.
independent six-membered rings such as in biphenyl, ter
phenyls, quaterphenyls and alkylated derivatives thereof,
or two or more fused aromatic rings as in naphthyl,
anthracene, phenanthrene, chrysene, pentacene, and the
The novel class of substituted aromatics to which this
invention relates has the following general formula:
like. Those containing only one aromatic ring are, of
course, derivatives of styrene, oc-methylstyrene, divinyl
benzene and di-(a-methylvinyl) benzene and their nuclear
alkylated derivatives.
Those containing two or more
aromatic rings, independent or fused, ‘are the vinyl and
a-vinyl derivatives of the corresponding aromatic hydro
carbons and their nuclear alkylated derivatives. The lat~
ter, the vinyl and u-methylvinyl derivatives of the poly
ring aromatics, can be prepared according to the process
wherein Ar is a mono or divalent aryl radical, R is hy
drogen or methyl, X is chlorine or bromine and n is 1 or 2.
These compounds are derived from the reaction of a
vinyl or alpha-methyl vinyl substituted aromatic com—
pound with a dichlorocarbene or dibromocarbene formed
in situ by the alkaline hydrolysis of chloroform or bromo
form. These dihalo carbenes are su?iciently stable and/ or
p-vinyl acetophenone, p-vinyl benzophenone, alkoxy
J.A.C.S., 80, S275 (1958). By opening the ring of the
of US. Patent 2,404,235 or according to the process de
scribed in the articles in J.A.C.S., 68, 1105—11l2. In ad
dition to the ar-nuclear substituted alkyl hydrocarbon
groups, there may also be present keto groups as in
form suf?ciently readily to react with the vinyl group: iii) groups as in methoxy styrenes, and the like.
The compounds of this invention are exceptionally use
ful because of the presence of the 2,2-dichloro- or 2,2-di
brornocyclopropyl groups. These groups may be reacted
as the same groups attached to an aliphatic chain. The
or a-methyl vinyl group:
preparation of such compounds from ole?ns and dichloro
carbene is described in J.A.C.S., 76, 6162 (1954), and
to form the 2,2-dichloro- or 2,2-dibromo-cyclopropyl or
2,2-dichloro- or dibromocyclopropyl group with a strong
l-methylcyclopropyl group. The reaction is accomplished
by combining the aromatic vinyl or u-methylvinyl com
acid such as H2804, hydrobromic, glacial acetic, and the
resulting mixture is heated to its boiling point and there
maintainedwith external heating until the reaction begins.
There is a short initiation period of about 10 to 30 min
utes during which the addition of heat to maintain re?ux
conditions is necessary. After the reaction begins, as
may be noted by the formation of sodium or potassium
without destroying the cyclopropane groups.
like, in a manner known to the art, there is ‘formed a
pound with an alkali metal alkoxide of a lower aliphatic 40 three-carbon aliphatic group which may be unsaturated
or which may contain the elements of the acid used to
alcohol; i.e., sodium or potassium methoxide, ethoxide,
open the ring. Also, the ar-alkyl 1-aryl-2,2-dichloro- or
t-butoxide, and the like, and an inert reaction solvent
dibromo-cyclopropanes can be oxidized to the correspond
such as a paraf?nic hydrocarbon. A small quantity of
ing aromatic mono, di and higher polycarboxylic acids
chloroform or bromoform is added to this mixture. The
chloride or bromide, the external source of heating can
be stopped since the reaction is exothermic and the re
mainder of the chloroform or brornoform added, pref~
erably slowly, to maintain a gentle re?ux. To insure good
contact between the reactants, the reaction mixture may
be stirred. The resulting reaction mixture is permitted to
reach ambient or room temperature. Water may be
added to dissolve the sodium or potassium chloride or
bromide by-product and to permit a separation of the
l-aryl dihalocyclopropane formed which is dissolved in
the reaction solvent. The resulting mixture is separated
into an organic phase and an aqueous phase as, for ex
ample, by settling and decantation. The two liquid phases
are separated. The aqueous phase may be extracted with
solvent such as the paraf?nic hydrocarbon employed as
the reaction solvent. The extracts and the organic phase
are combined, dried, if desired, and the l-aryl dihalo
cyclopropane is recovered, for example, by distillation
unique acids and their preparation are more ‘fully de
scribed in our copending application Serial No. 849,752,
?led October 30, 1959, and now abandon-ed.
In order to facilitate a clear understanding of the in
vention, the process ‘for preparing the novel substituted
aromatic compounds is illustrated by the following de
tailed description.
Example 1
l-(p-tolyl)-2,2-dichlorocyclopropane is prepared in the
following manner. A three liter, 3-neck ?ask equipped
with a stirrer, condenser and dropping funnel is charged
with 3 moles (162 grams) sodium methoxide, 500 milli
liters pentane as the reaction solvent, and 2.77 moles (354
grams) p-methylstyrene. Three moles (360 grams) of
chloroform are added to the dropping funnel and 30 mil
liliters of chloroform are added to the ?ask. The mixture
in the ?ask is heated to its boiling point and maintained
under re?ux conditions until the reaction is initiated. The
heat source s removed and chloroform is added dropwise
at a rate to maintain a gentle re?ux, about three hours.
After the addition of chloroform is complete, the resulting
mixture is stirred at room temperature overnight. To the
resulting mixture there are added 800 milliliters of water.
or by evaporation of the solvent associated therewith.
The l-aryl dihalocyclopropane can be further purified by 70 The mixture is permitted to separate into two phases. The
fractionation when feasible or by extraction or recrystal
lization when applicable.
Water phase is extracted with pentane. The pentane ex
tracts and the organic layer are combined and dried over
anhydrous magnesium sulfate. The dried material is dis
and found to be in close agreement with the correspond
tilled to recover p-methyl-1-(2,2-dichlorocyclopropyl)
benzene with boiling point 122° C. at 12 mm. Hg and re
cates :
ing calculated values for Cwl-lmClz as the following indi- v
fractive index nDZ" 1.5460. By analysis of this compound
the carbon, hydrogen and chlorine content was deter—
mined and found to be in close agreement with the corre_
sponding values calculated for CmI-I10Cl2 as the following
.13 y analy- Calculated,
sis, percent
Carbon _____ __
58. 7
Hydregen__ __
5. 26
Chlorine. _ _ __
59. 7
4. 98
35. 3
By an aly- Calculated,
sis, percent
Carbon ______________________________________ __
60. 3
5. 28
Chlorine ____________________________________ __
35. 2
Example 5
By repeating the process of Example 1 employing 480
grams of p-isopropyl-a-methylstyrene in place of 354
grams p-methylstyrene, there was obtained l-methyl-l-p
59. 7
4. 98
35. 3
cumyl-2,2-dichlorocyclopropane with boiling point 133°
Example 2
20 C. at 9 mm. Hg and refractive index nD2° 1.5291. By
By repeating the process of Example 1 employing 284
analysis of this compound the carbon, hydrogen and chlo
grams styrene in place of 354 grams p-methylstyrene,
there was obtained by the distillation of the dried pentane
rine content was determined and found to be in close
agreement With the corresponding calculated values for
C13H16Cl2 as the following indicates:
solution 1-phenyl-2,2-dichlorocyclopropane with boiling
point 103° C. at 10 mm. Hg and refractive index nDZ" 25
1.5508. By analysis of this compound the chlorine con
tent was determined and found to be in close agreement
with the corresponding values calculated for C9H8Cl2 as
the following indicates:
By analy- Calculated,
sis, percent percent
Hydrogen ___________________________________ __
Chlorine ____________________________________ ._
63. 6
63. 9
7. 12
29. 1
6. 97
29. 1
By analy- Calculated,
sis, percent percent
Example 6
Chlorine ____________________________________ __
37. 9
38. 0
By repeating the process of Example 1 employing 480
grams m-isopropyl-a-methylstyrene instead of 354 grams
p-methylstyrene, there was obtained l-methyl-l-m-cumyl
Example 3
The process of Example 1 is repeated except that354 40 2,2-dichlorocyclopropane with boiling point 135° C. at 11
mm. Hg and refractive index 111320 1.5249.
grams (2.77 moles) mixed meta and para vinyl toluenes,
60% meta and 40% para, are employed in place of p
Example 7
methylstyrene. The dried combined pentane extracts and
(2,2-dichlorocyclopropyl) benzene
organic layer are distilled to remove the pentane. The
residue is distilled at 10 mm. Hg. There are collected 45 having the formula:
86.6 grams of a fraction boiling in the range of 114-1 17°
C. This material is fractionated through an Oldershaw
column and a center cut boiling at 115°~116° C. at 10
mm. Hg is taken. This center cut has a refractive index
nD2° 1.5458. By analysis of this center cut the carbon, hy
drogen and chlorine content was determined and found to
may be prepared by stirring and heating a mixture of 130
be in close agreement with the corresponding calculated
grams (1.0 mole) divinyl benzene, 230 grams (2.05
values for CmHmclz as the following indicates:
moles) potassium tert. butoxide, 50 grams chloroform and
800 grams heptane to its boiling point and maintained
under re?ux conditions until the reaction is initiated.
Thereafter, external heating is stopped and 265 grams (2.1
moles) of chloroform are slowly added to maintain a
By analy- Calculated,
sis, percent percent
60. 1
5. 29
59. 7
4. 98
Chlorine ____________________________________ __
35. 3
35. 3
gentle re?ux. After completion of the chloroform addi
tion, the reaction mixture is stirred until its temperature
60 cools to 25° C.
Water is added to the mixture to dis
solve the solids formed. The aqueous layer and organic
layer are separated. The aqueous layer is extracted with
heptane. The extracts and organic layer are combined,
By oxidation of the center cut it is found that the prod 65 dried and distilled to remove heptane. The residue may
be puri?ed by fractionation.
uct of this process contains l-(m-tolyl)-2,2-dichlorocyclo
propane (60%) and l-(p-tolyl)-2,2-dicl1lorocyclopropane
Example 8
(40% ).
By the procedure of Example 1 or 7, there may be pre
Example 4
pared 4-(2,2-dichlorocyclopropyl) biphenyl:
By repeating the process of Example 1 employing 354 70
grams of a-methylstyrene in place of p-methylstyrene,
there was obtained l-methyl-1-phenyl-2,Z-dichlorocyclo
propane with boiling point 92° C. at 6 mm. Hg and refrac
tive index nD2° 1.5400. By analysis of this compound the
carbon, hydrogen and chlorine content was determined 75
Product structural formula and name
Vinyl Aromatic
l-vinylnaphthalene _____________ __
\ /
We claim:
3. A 1-tolyl_2,2-dichlorocyclopropane having the for
1. An aromatic dihalocyclopropane having the formula:
L \ G / \H
X/ \X
wherein Ar is an aromatic hydrocarbon radical Whose
valence corresponds to the value of 11 selected from the
4. A l-xy1yl-2,Z-dichlorocyclopropane having the for
class consisting of alkyl substituted phenyl radicals, the 25 mula:
divalent phenylene radical, aromatic hydrocarbon radi
cals containing more than one independent joined 6
membered aromatic ring, aromatic hydrocarbons contain
ing fused rings, and alkyl hydrocarbon derivatives of
these multi-ring aromatics, R is a member selected from
the class consisting of hydrogen and an alkyl hydrocar
5. p-Di-(2,2-dichlorocyclopropyl) benzene having the
bon radical, X is a halogen selected from the class con
sisting of chlorine and bromine and n is an integer from
1 to 2.
2. l-(p-Biphenyl)-2,2-dich1orocyclopropane having the
References Cited in the ?le of this patent
Skell et aL: J. Am. Chem. Soc. 78, 5430-3, 1956.
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