close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2127107

код для вставки
2,127,107
Patented Aug. 16, 1938
UNlTED STATES
PATENT OFFICE
. 72,127,107
PROCESS OF ‘PRODUCING’. coERoxENoL
ESTERS
‘
Thomas A. Cassidy, Brooklyn, N. Y., a's'signor to
Wilmot and Cassidy, Inc., Brooklyn, vN. Y., a
corporation of New York
No Drawing. Original application July 24,1934,
Serial No. 736,631. Divided and ‘this applica
tion October 3, 1936, Serial No. 103,911
8 Claims.
(01. 260-335)
This application for patent is a division of an
in and impart ?uorescence thereto, as above
application ?led by me July 24, 1934, Serial No.
stated, but that vthey possess the other qualities,
736,631, which is a continuation in part of an
above enumerated, necessary to render their use
for this'purpose commercially practicable.
application for patent ?led by me August‘ 23,
vi
I,
have, ‘for example, found that dimethyl 6,12-‘ v~5
1932, Serial No. 630,087.
‘
'
The present invention relates to a process for coeroxenolaceta'te, when produced by the process
producing ?uorescent dyes soluble in high boiling‘ herein-afterdescribed, ‘meets all the most exacting
aliphatic and aromatic hydrocarbons, particularly
However, known processes for producing or-_
lubricating oil, and more particularly to certain
dyes of the heterocyclic group containing oxygen ganic Compounds of the coeroxene class do noti‘lio
produce these compounds, including the speci?c
in the ring.
requirements.
'
Y
>
compound just above mentioned,’ in a form en
In marketing petroleum products such as motor
fuels, lubricating oils, etc, it is customary to add
certain dyes to these products in order that the
purchasers may distinguish between the different
tirelyacceptable for addition to lubricating oils.
The present invention comprises an improved.‘
‘method of producing these compounds, par- “r5
ti‘cularly applicable to the production of 6,12
brands. In some cases several manufacturers
use the same color or different shades of the same
dimethyl coeroxenol acetate and other substituted
coeroxenol esters, whereby a ‘high yield of the
compound may be produced in its purest state
color, thereby making it difficult for the pur
chaser to know whether or not he is getting
the products he orders. The producers, who are
and in a form which renders its use as an addi-ii‘g’o
marketing arti?cially colored products, are loath
tion to lubricating oils highly efficient to produce
to change the colors of their products, and in
some cases‘it is impracticable to do, as certain
the desired green ?uorescence and ineffective to
impart to the oil any undesirable characteristics.
1 In manufacturing the improved product I pro
colors are now Widely used to designate certain
25 qualities. Again,‘it is not desirable to color cer
tain petroleum products, as such coloring would
destroy their sales value, the products being
graded by their natural colors.
'
7
One vway to distinguish from one anotherdif
ferent brands having the same color is to im
part fluorescence of different hues to these prod
ceed as follows, it being understood that those“2
skilled in the art may deviate, without the exer
cise‘ of invention, from the precise details of the
prescribed steps, vwhich are preferable rather
than mandatory. It will also‘ be understood that
> ‘the described speci?c. process is intended for the 30
production of 6,12-dimethyl coeroxenol» acetate
vand that obvious modifications of the process are
ucts, thereby giving them distinguishing char
necessary for the production of other organic
color compounds of the coeroxene class.
acteristics without substantially altering ' their
colors as viewed by transmitted light.
case
of
lubricating
In the
oils, imparting a green
fluorescence actually enhances the value.
' "To a molten mass comprising 220 pounds of; 35
1 paracresol (or a meta or para'substituted phenol)
There are many known dyestuffs which'will
impart fluorescence to valcohol ‘and water and
and 150 pounds of phth-alic anhydride are added
90 pounds of concentrated sulfuric acid or other
condensing agent such as phosphorous pentoxidek v
740
fluorescence to, lighter petroleum hydrocarbons; zinc chloride or stannic chloride.
1 The mix is then heated with agitation to about
but few, if any, are known to be soluble in, and
adapted to impart ?uorescence to, lubricating oils ' 160° C. and maintained at that temperature for
and which at the same time are known to be “about ?ve hours. At the conclusion of this heat
stable to light, heat and storage-to be unaffected . ing step the mass is dumped into (say) 300’
some are known to be soluble in, and impart
by metals, to be'completely neutral in reaction
and not to impart to such oils any qualities which
would make them commercially impracticable.
Certain dyestuffs'of the heterocyclic group con -
gallons of water to which is added 100 pounds of 5'45
taining oxygen in the ring which are free from
soluble material which it then contains is sepa
rated by iiltration and dried. This insoluble ma-'- ‘50
nitrogen and sulphur, namely, organic com
pounds of the coeroxene class (by which term I
mean to include coeroxene, its derivatives and
caustic soda or any other strong base such as
caustic vpotash or'lithium hydroxide. This mix
is then boiled for about one hour and the in
terial is an intermediate product dimethyl 2,7.
fluoran and amounts to 200lbs.
.
100 pounds of the dimethyl 2,7-?uoran (or any
substitution products) I have found to be soluble
in and effective to impart ?uorescence of‘ different ‘ di-substituted 2,7- or 3,6-?uoran produced by the
procedure above described by or any obvious vari- 5'5
shades of green and of varying degrees of intens
ity to both aliphatic and aromatic hydrocarbons. ation thereof) is added to 700 pounds of fuming
So‘ far as I know, none of the dyestuifs of the sulfuric acid (oleum) at 20°-25° TC. and the mix
class mentioned have ever been added to com- _ .is- continuously agitated for about eight hours,
mercial lubricating oil.“ ‘When ‘added thereto I after which it is diluted by pouring into 1200
60 have found that'they are not only soluble there pounds of water to'which ‘has been added‘about $60
2
2,127,107
an equal weight of ice. The product is a sub?
stituted coeroxonol ‘sulfate-speci?cally, follow
eroxenol ester of high purity and yield and suit
able for addition to lubricating oil to impart
fluorescence thereto which comprises reducing a
solution of dimethyl 6,12-coeroxonol sulphate.'_ 1 , substituted coeroxonol in an alkaline medium
To this product is added 900 poundsof 28% containing an organic solvent soluble in water
ammonia, 1800 pounds of ice and 1200 pounds of and that does not react with the subsequently
ing the precise procedure above described, a red
water, whereby the dimethyl 6,12-coeroxonol base
is precipitated. It is of alight grey color. When
dried the yield of the base is 95. pounds. -
10
added esterifying agent and then esterifying.
2, The process of producing dimethyl 6,12
coeroxenol acetate of high purity and yield which
After the dimethyl 6,12-coeroxonol base is ob
tained the‘ heterocyclic compound dimethyl c0
eroxene may be obtained‘ by reducing the base.
This heterocyclic compound, its substitution prod
ucts and derivatives, as well as its isomers and
' homologues, produce a green ?uorescence when
dissolved in aliphatic or aromatichydrocarbons.
For instance, dimethyl 6,12-coeroxenol, its isomers
and homoiogues may be used as well as the
acetates, benzoates, phthalates or any organic
20 acid ester, of dimethyl 6,12-coer0xenol and its
isomers or homologues. Dimethyl 76,12_-c0
comprises reducing dimethyl 6,12-coeroxonol in 10
an alkaline medium containing an organic sol
vent soluble in water and that does not react
with acetic anhydride and then esterifying by
addition of acetic anhydride.
3. The process of producing dimethyl 6,12 15
coeroxenol acetate of high purity and yield which
comprises treating dimethyl 6,12-coeroxonol with
pyridine, caustic alkali and zinc dust and ester—
ifying by the addition of acetic anhyride.
4. The
process of producing a
substituted 20
coeroxenol ester of high purity and yield which
,eroxenol is not as stable to heat and light as are - comprises treating a di-substituted fluoran with
dimethyl 6,12-coerox'ene and the derivatives and sulphuric acid and thereby producing a sub
substitution products ofdimethyl 6,12-coeroxeno1
25 so that its use,v is not recommended when any of
the other products herein mentioned are avail
able.
r
in the knowledge of those skilled in the art to ob
30 tain the above-mentioned derivatives and sub
stitution productsand also others not mentioned
‘which will impart a fluorescence to aliphatic
and aromatic hydrocarbons. However, I believe
it to be impossible, by the employment of any
35 known process, to secure a commercially econom~
ical yield or to secure a product of satisfactory
purity, strength, color, or stability to heat or in
not react with the subsequently added esterifying
agent, and then esterifying to producethe sub~
stituted coeroxenol ester.
30
5. The process of producing a substituted co
eroxenol ester of high purity and yield which
comprises treating a di-substituted ?uoran with
sulphuric acid and thereby producing a sub
stituted coeroxonol sulphate, precipitating the 35
substituted coeroxonol base, reducing the coer
oxonol base in an alkaline medium containing
storage. The following procedure for obtaining
the dimethyl 6,12-coeroxenol acetate mentioned
pyridine and esterifying by the addition of acetic
has been found to overcome all the objections in
ample the dimethyl 6,12-coeroxonol base-is ob
6.'The process of producing dimethyl 6,12
coeroxenol acetate of high purity and yield which
comprises treating dimethyl 2,7-?uoran with sul
furic acid and thereby producing dimethyl 6,12
tained, 100 pounds ofthe same are mixed with
coeroxonol sulphate, precipitating the dimethyl
herent in known processes.
.
After the coeroxonol base—in the speci?c ex
45 400 pounds of water, 40 pounds of caustic soda
or other strong base and 280 pounds of pyridine,
or equivalents thereof, e. g., methyl pyridines
(picolines), dimethyl vpyridenes (lutidines) or
other organic solvents soluble in water that do
not react with acetic anhydride, such as acetone
and dioxan. The mixture is heated to 90° C. and
agitated.
“
_
Thereafter is added 30 pounds of ‘zinc dust or
iron powder. The entire mixture is then agitated
for about two hours at 90° C. and cooled to 30° C.
after which there is added slowly a suitable acid
esterifying agent, such as acetic anhyride, pro
pionic anhydride, butyric anhyride or benzoyl
chloride.
The mixture is maintained for about
60 two hours at 30° C. and is added to 400 gallons
‘of water, ?ltered and the product washed and
dried. Assuming the addition of the preferred
acid esterifying agent-acetic anhydride—the
yield is 70-100 pounds of dimethyl‘6,l2 coeroxenol.
65
substituted coeroxonol base, reducing the co 25
eroxonol base in an alkaline medium containing
an organic solvent soluble in water and that does
.
After thecoeroxonol base is obtained it is with
.40
stituted coeroxonol sulphate, precipitating the
acetate.
\
The pyridine orequivalent bases play a dual.
role, one that of acting as a solvent for the co
anhydride.
-
6,12-coeroxonol base, reducing said base in ad 45
mixture with water, caustic alkali and pyridine,‘
and esterifying by the addition of acetic anhy
dride.
7. The process of producing dimethyl 6,12
coeroxenol acetate of high purity and yield which 50
comprises melting together paracresol and
phthalic anhydride, adding sulphuric acid, treat
dual role of pyridine plays an extremely impor
What I claim and desire to protect by Lettersv
Patent is?
, 7.5
1. The process of producing a substituted co
'
ing the mix with caustic alkali to thereby produce
as an intermediate product dimethyl 2,7-fluoran,
treating said intermediate product with sulfuric 55
acid and thereby producing dimethyl 6,12
coeroxonol sulphate, precipitating the dimethyl
6,12-coeroxonol base, reducing said base in ad
mixture with water, caustic alkali and pyridine,
and esterifying by the addition of acetic anhy
dride.
V
8. The process of producing dimethyl 6,12
coeroxenol acetate of high purity and yield which
comprises treating approximately 220 parts of
paracresol and 150 parts of phthalic anhydride 65
with a condensing agent, and treating the re
.sulting mixture with caustic alkali to thereby
produce dimethyl 2,7-?uoran, treating said in
termediate product with sulphuric acid to pro
eroxonol base to facilitate reduction and the other‘
that of a carrier or catalyst for the esterifying'
70 agent (acetic anhydride or equivalent). This 1 duce dimethyl 6,12-coeroxonol sulphate, pre
tant part in the process.
‘
cipitating the dimethyl 6,12-coeroxonol base, re
ducing said base in admixture with water, caustic
alkali and pyridine, and esterifying by the addi
tion of acetic anhydride.
THOMAS A. CASSIDY.
Документ
Категория
Без категории
Просмотров
0
Размер файла
358 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа