MURRAY SENKUS
10
8-Nitro-isobutyloxy-dihydro-cxP.dicyclo entadiene.-
Boron trifluoride-diethyl ether (40 9.) was agded dropwise to a stirred solution of 178.5 g. of 2-nitro-isobutyl alcohol, 198 g. of dicycFpentadiene and 200 cc. of ethylene dichloride a t 50 . The temperature was maintained a t 60-55' by cooling with ice water. The time required for the addition was thirty minutes. After the exothermic reaction had ceased, the mixture was warmed for six hours at 40-50' then cooled, washed with water and dilute soda solution, followed by a water wash. The product after drying yielded 212 g. of the crude nitro ether as a colorless oil boiling a t 1.60-180' (5 mm.). Upon refractionation this gave 169 g. of the pure product boiling at 136-137' (0.4 mm ). Phenoxy-dihydro-ero-dicyc1opentadiene.-To a stirred mixture of 132 g. of dicyclopentadiene and 94 g. of phenol there was added dropwise during the course of thirty minutes 18 g. of 98% sulfuric acid while the reaction mixture was maintained at 28-32' by a cold water-bath. The mixture was stirred thereafter for two hours, then
Vol. 68
poured into hot water. The oil layer was separated and washed thoroughly with hot water and soda solution. The washed oil was dried, mixed with 1%of its weight of dry sodium carbonate and distilled in vacuo. The fraction boiling at 140-150" (1 mm.) was a pale yellow oil. The yield was 98 g. On standing it solidified to a crystalline mass which after recrystallization from methanol Tith the aid of Norite formed colorless crystals, m. p. 70-71 .
summary 1. Alcohols and phenols add to dicyclopentadiene in the presence of acidic catalysts (BF8 or H2S04) to yield rearranged unsaturated ethers, which are derivatives of hydroxy-dihydro-cxodicyclopentadiene. 2. The lower aliphatic ethers thus obtained possess intense floral odors. PHILADELPHIA, PBNN.
RECEIVEDSEPTEMBER 5, 1846
[CONTRIEIUTION FROM RESEARCH A N D DEVELOPMBNT DEPARTMENT, COXbfERCIAL SOLVENTS CORPORATION]
Reaction of Primary Aliphatic Amines with Formaldehyde and Nitroparaffins* BY MURRAY SENKUS In spite of the reports mentioned above which Henry's2 has shown that nitromethane reacts with N-hydroxymethyldimethylamineto give 2- indicated that N-hydroxymethylisopropylamine nitro-l,3-bisdimethylaminopropaneand with N- would not react with 2-nitropropaneJ the reaction hydroxymethylpiperidine to give 2-nitro-1,3-bis- was tried. The two compounds reacted smoothly (N-piperidyl)-propane; also that N-hydroxy- a t room temperature to give N-(2-nitroisobutyl)methylpiperidine reacts with nitroethane to give isopropylamine in 76% conversion. In view of 2-nitro - 2 -methyl- 1,3- bis (N -piperidyl) -propane this result the reactions of other N-hydroxyand with 3-nitro-1-propanol to give 2-nitro-2- methylmonoalkylamines and other nitroparafhs (2- hydroxyethyl) - lJ3-bis-(N-piperidyl) -propane. were investigated and are reported in this paper. It was also found that N-(2-nitroisobutyl)-isoMousseta allowed N-hydroxymethylpiperidine to react with 1-nitro-3-methylbutane and isolated 2- propylamine can be prepared from 2-nitro-2nitro-2 - (2-rnethylpropyl) - 1,3-bis- (N-piperidyl)- methyl-1-propanol and isopropylamine. Presumpropane. Duden, Bock and Reid' repeated ably the nitro alcohol in the presence of the amine Henry's synthesis of 2-nitro-l,3-bisdimethylamino- yields 2-nitropropane and formaldehyde. The propane and reduced the nitro amine with stannous aldehyde and isopropylamine yield N-hydroxychloride to 2-amino-1,3-bisdimethylarninopropane. methylisopropylamine which then reacts with 2They tried to condense N-hydroxymethylamine nitropropane as above. Some other nitro amines with nitromethane, but with no success. More re- were prepared from primary amines and nitro cently CerP made an extensive study of the reac- alcohols derivable from nitroparafhs and formtion of nitroparaffins with products derivable from aldehyde and are reported in this paper. The nitro amines which were prepared were aldehydes and amines and from formaldehyde and amides and on the basis of his work concluded that hydrogenated to the corresponding polyamines. only 2 moles of a N-hydroxymethyldialkylamine These hydrogenations are also described herein. will react with nitromethane and only one mole Experimental of a N-hydroxymethyldialkylamine will react I. Preparation of Some Nitro Amines from Secondary with any other primary nitroparaffin. The latter Nitroparaf?ins conclusion was in contradiction to Henry's and Two methods were developed for the preparation of Mousset's results. Cerf also concluded that N- nitro amines from secondary nitroparaffins. These hydroxymethyldialkylamines do not react with methods are described below and the preparation of N-(2secondary nitroparaffins and that N-hydroxy- nitroisobuty1)-isopropylamine is used as an example. Method A. From Isopropylemine, Formaldehyde and methylmonoalkyIamines do not react with either 2:Nitropropane.-Two moles of isopropylamine (118 9.) primary or secondary nitroparaffins. was placed in a two-liter, three-necked flask fitted with a
-
* Prepared lor the September, 1945, Meeting-in-print.
(1) Henry, Bn.,18, 2027 (1905). (2) Henry, Bull. =ad. IOY. Bslz., [3] 88, 412 (1897). (3) Mou8set. ibid., 621 (1901). (4) Duden, Bock and Rdd, B e . , 11,2036 (1906). (61 carf. BYu. CLW, 1614, iui (1011); 1814, iuw (igai),
=.
condenser, a sealed stirrer, a dropping funnel and a thermometer reaching into the liquid. The flask was immersed in a water-bath, the temperature of which was maintained at 17-20'. Two moles of 36% (by weight) aqueous formaldehyde was added slowly to the h k whlle the mixture ww qhtmd.. Thr tempatrue ofthe mixture
Jan., 1946
-Y
s WITH FORMALDBWDE m~ NITROPARAFFINS
ALIPHATIC a
11
TAFJLB I SOMENITROAmms Con- Method Stuting mateciala P Amine Nitropuuffin %Nitropropane 0 Methylamine
R
M Isopropylamine A L D Is~propylrmjne
B H Isopropylamine Y D E rmpropylamine
__
V".
nf
produet slon prepn. A 48 N-(%Nitrohbutyl)methylmine A Nitrocthane %Nitro-%methyl-l.3- 71 B diiapropyl.mio080 prom A ZNitmpropdnc N-(%Nitroiaohtyl)76 86 B L0proPY-e I-NitroprOpOne %Nitro-2-~thYl-1,3*proPYl=li-
Pc0P-e' N-(%Nitro-%methylbutyl)-iaopropyl-
Boilingpt. OC. Mm. n% d% Formula 60-82 6 1.4368 1.0166 OHuNrO,
Nitrogen, % Calcd. Pound 21.20 21.02
88-100
3
1.4618 0.9671 CaHriNtOl
19.34
84
10
1.4339 0.9686 C~HiiNiCh
17.49 17.34
96-97
10
1.4409 0.8626 ClHnN;O,
16.08 16.09
1.4407 0.9684 CEHIBN:OI
16.08 15.95
10
1.4384 0.9571 C~HIIN:O,
16.08 16.17
2
1.5178 1.0785 CuHitNiO:
13.45 13.59
19.31
90
A
85
A
72
A
76
B
130-133
so
B
74.90
2-Nitropropane N-(%IGtrohobutyl)-l- 75 1-Phcnylethylphenylethylamine d e O-Amino-2-methyl- 2-Nitropropane N-(2-Nitroisobutyl)-2- 90 &no-2-methyl-11-propanol PioF-0~ 2-Amino-1-bi1tPnol 2-Nitropropane N-(%Nitroirobuty1)-2- 10 .mino-l-hutPnol
B
121-124
A
59.v
CaHuNrOl
14.73 14.84
A
58.1"
GHeN&
14.73 14.49
ZNitrobutrrnc
amine
Butylamine
2-Nitropropsne N-(%Nitrohbutyl)-
106-107 10
butylamine 1-MethylpropylDmlnC
Benzylamine Benzylamint
2-Nitropropane N-(%Nitrohbutyl)-lmethylpropyruninc 2-Nitropropu~e N-(%Nitroisobutyl)mlIUQiUe Chloronitro 2-Nitru-2-chlor0-1,3methane dibenzylamino-
96
CI~H:ONIO,CI10.62c 10.75O
Proppne
0
a Melting point. *Purification of material was not attempted. Chlorine content.
0 . 8 1 . W 1.0809 CuHirNiOr
12.60 12.85
Crude material was reduced to the polyamine.
TABLEI1 SOME POLYAMINES Polyamine
N-(2-Aminoisobutyl);methylamime 2-Amino-2-methyl-l.3-diisopropylaminopropane N- (2-Aminoisobutyl)-bopropylamine 2-Arnin0-2-ethyl-l.3diisopropylaminopropane N-(2-Aminoisobutyl)-butylamine N-(2-Aminoisobutyl)-1-methylpropylamine N-(2-Amin~~2-methylbutyl)-isepropylamine N-(2-Aminoisobutyl)-benzylamine N- (2-Aminaisobutyl)-1-phenylethylamine N-(2-Aminobobutyl) -2-aminw2-methyl-1-propanio1 N-(2-Aminoisobutyl)-2-amino-1-butanol
Boiling point OC. Mm.
123 98-100 147.3 71-72 64-66 56-58
67.5 105-106 110 115-116 118-121
was not allowed to exceed 25' during the addition of the aldehyde. Two moles of 2-nitropropane (178 g.) was added to the flask a t one time and the mixture was s h e d for thirty minutes without further cooling. Twenty grams of sodium sulfate WBS added to the mixture and stirring was continued until the salt had dissolved. The nonaqueous layer was separated from the water layer and was allowed t o stand in the room for five days. A small additional amount of water separated from the crude product on standing. Distillation of this product through a fourfoot laboratory column gave 26 g. of material, b. p. 3445" at 10 mm. and a42 g. of N-(2-nitroisobutyl)-~r0pylm i n e . b. p. 85' a t 10 mm. The distillation was discontinued a t thii point because the residue (36 9.) began to decompose. Conversion to nitro amme was 76%. Method B. From 2-Ritro-2-methyl-l~p 01 m d Ieopropylam.ine.-+e mole of i s o p r o p y l a m m ~ g . )and one mole of 2-nitro-2-methyl-l-propanol (119 8.) were placed in a glass-stoppered bottle and the mixture was shaken until it had become hamogeneous. The solution was allowed to stand at room temperature. Water began
750 3 760 1 10 10 10 8 5 10 10
U'*D
dlo,
1.4293 0.8149 1.4502 .8596 1.4263 .8025 1.4491 .8520 1.4346 .8154 1.4297 .8171 1.4348 .8166 1.5153 .9526 . . . . .9373 1.4651 .9380 1.4631 .9343
Formula
CaHidN2
Nitrogen, Calcd. Found
27.42 22.43 CrHisNt 21.51 CeHnNs 20.87 CeHpNt 19.42 CCHmN2 19.42 C&mNt 19.42 CjiHiaNz 15.71 CiiHf~Nt 14.57 C&oNtO 17.48 CfimN10 17.48 CsHaNs
27.38 22.36 22.06 20.87 19-.23 19.41 19.23 15.52 14.37 17.29 17.05
t o separate as a lower layer after ten hours. The separation of water ceased after three days. The top layer was distilled through a column a t reduced pressure. Conversion to nitro amine was 86%. XI. Preparation of Some Nitro Diamines from Primary Alkyl Amines and Primary Nitropara5ns Two methods were developed for the preparation of nitro diamines from primary amines, formaldehyde and primary nitroparaffins. The preparation of 2-nitr0-2methyl-1,3-diisopropylaminopropane according t o each of those methods is described below for illustration. Method A. From Isopropylamine, Formaldehyde and Nitroethane.-Two moles of isopropylamine and two moles of formaldehyde were mixed as above. One mole of nitroethane (75 g.) was added to the mixture w i t h agitation over thirty minutes. Twenty grams of sodium sulfate was added and stirring was continued until the salt had dissolved. The non-aqrieous layer was separated from the water layer and was allowed to stand over 5 g. of anhydrous sodium sulfate for three days. The mixture was
HUG. JOHNSON
12
filtered and the filtrate was distilled at 3 mm. Yield of 2-nitro-2-methyl-l,3-diisopropylaminopropane, b. p. 98100” at 3 mm., was 161 g.; conversion, 71%. Method B. From 2-Witro-2-methyl-1,3-propanediol and Isopropylamine.-A solution of one mole of 2-nitr0-2methyl-1,3-propanediol (135 g.) and two moles of isopropylamine (118 g.) was allowed t o stand in the room for three days. Distillation of the top layer gave 137 g. of nitro diamine; conversion, 60%.
III. Hydrogenation of Nitroamines to Polyamines The nitro amines which were prepared were hydrogenated t o the corresponding polyamines. The hydrogenation of each nitroamine and the isolation of the products were carried out as follows: One hundred grams of nitroamine (either pure nitroamine or crude nitroamine which had not been rectified) was dissolved in 100 ml. of methanol and the solution was hydrogenated a t 30-50’ and 600 lb./sq. in. in the presence of 6 g. of Raney nickel. The solution was filtered and the filtrate was distilled at atmospheric pressure t o remove the methanol. To the residue was added 200 ml. of benzene. A Dean and Stark moisture trap6 which was connected t o a condenser was fitted to the top of the column and the mixture was refluxed until water had ceased separating in the trap. Distillation of the residue was then resumed. The conversion t o pure polyamines, basis nitroparaffins, was the same whether the pure nitro amines or the crude nitro amines were hydrogenated. Lists of nitroanlines and polyamines prepared together with some of their properties are given in Tables I and 11.
Summary It has been found that N-hydroxymethylalkylamines derivable from primary alkyl amines and formaldehyde will react with secondary nitroparaffins according to the following scheme
Vol. 68 R
I I
R’NH-CHz-C-NO, R
It was shown that N-hydroxymethylalkylamines will react with primary nitroparaffins to give nitro diamines BR’.NHCH*OH
+ R CHzNOz + R
I R’NH -CH2-C--CH2--NH-Rf NO2
The above nitro compounds were also prepared by allowing the primary alkylamines to react with nitro alcohols derivable from the same nitroparaffins and formaldehyde according to the following schemes R
+
I
R ’ N H ~ HOCH~-C--NO~
I
R R’-NH-CHz-C--NO,
R I
2R‘NHs
+ HOCH2-C-CHzOH I
+
I R’NH-CHz-C-CHz-NH-R’
+ 2Hz0
The nitroamines that were prepared were hydrogenated to the corresponding polyamines.
I
FROM
4-HzO
NOz.
--f
(6) Dean and Stark, Ind. Eng. Chrm., 13, 486 (1920).
[ CONTRIBU’TION
1 I
R
1
R
-
+
R
I
+ I-I--C-NOz
+ 2Hz0
I
R K’NHCI-I,OII
+ HzO
TERRE HAUTE,INDIANA RECEIVED AUGUST22, 1945
RESEARCH A N D DEVELOPMENT DEPARTMENT, COMMERCIAL HAUTE,INDIANA]
SOLVENTS
CORPORATION, TERRE
Reaction of Aliphatic Amines with Formaldehyde and Nitroparaffins. 11. Secondary Amines* BY HALG. JOHNSON’ Essentially the results of the work described in this paper are an extension of the work of Senkus and also Henry, Mousset and Cerf as described in the preceding article. The secondary nitroparaffins have been treated with formaldehyde and various aliphatic secondary amines. However, some primary nitroparaffin reactions with formaldehyde and secondary aliphatic amines also have been covered. The reaction was carried
*
Prepared for the 1945 Meeting-in-Print of the Division of Organic Chemistry, ACS. For part I see Senkus, THISJOURNAL, 88, 10 (1946). (1) Presently associated with the Dykern Company, St. Louis, Missouri.
out by two different methods: A, reaction of the amines, formaldehyde and nitroparaffin ; and B, reaction of the amine with the nitro alcohol or iiitro diol. Although the same end-products result in either case, it is believed that the nitro alcohol or the nitro diol first decomposes into the nitroparaffin and formaldehyde. The relative rates of reaction are considered an indication of the mechanism. The nitro amines which were prepared were all hydrogenated to the corresponding polyamines. These reduction products are also described here.
